JPS6222830A - Silicon-containing polyimide resin and its production - Google Patents
Silicon-containing polyimide resin and its productionInfo
- Publication number
- JPS6222830A JPS6222830A JP16265985A JP16265985A JPS6222830A JP S6222830 A JPS6222830 A JP S6222830A JP 16265985 A JP16265985 A JP 16265985A JP 16265985 A JP16265985 A JP 16265985A JP S6222830 A JPS6222830 A JP S6222830A
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- Japan
- Prior art keywords
- polyimide resin
- tetrahydrophthalic anhydride
- diamine
- silicon
- mol
- 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.)
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
本発明は、ポリイミド樹脂及びその製造法に関するもの
であり、詳しくは耐熱性、密着性、接着性及び耐摩耗性
に優れ、電気絶縁材料、コーティング材料、接着材料及
び含浸材料等として有用な構造式〔Ｉ〕の４位に各種シ
リル基を有する１、２，３．４−テトラヒドロ無水フタ
ル酸を反応させて得られる新規な珪素含有ポリイミド樹
脂及びその製造法に関するものである。Detailed Description of the Invention (a) Industrial Application Field The present invention relates to a polyimide resin and a method for producing the same. Specifically, it is an electrically insulating material that has excellent heat resistance, adhesion, adhesion, and abrasion resistance. , a novel silicon-containing polyimide obtained by reacting 1,2,3,4-tetrahydrophthalic anhydride having various silyl groups at the 4-position of structural formula [I], which is useful as a coating material, an adhesive material, an impregnating material, etc. It relates to resins and their manufacturing methods.
（ロ）従来の技術
ポリイミド樹脂は、引張強度及び強靭性等を始めとする
機械強度、耐薬品性並びに電気絶縁性等に優れた耐熱性
樹脂として知られている。(b) Prior Art Polyimide resins are known as heat-resistant resins that are excellent in mechanical strength, including tensile strength and toughness, chemical resistance, and electrical insulation properties.
このポリイミド樹脂は、耐熱性フィルム、接着剤、゛コ
ーティング剤、成形用樹脂及び積層用樹脂として使用さ
れ、近年電気或いは電子材料、宇宙航空材料、自動車部
品及び特殊機器部品等への応用が盛んになりつつある。This polyimide resin is used as heat-resistant films, adhesives, coating agents, molding resins, and laminated resins, and in recent years has been increasingly applied to electrical and electronic materials, aerospace materials, automobile parts, and special equipment parts. It is becoming.
特に、電気或いは電子材料等の分野においては、エナメ
ル電線被覆剤、銅張印刷回路基板用フィルム、絶縁フィ
ルム或いはシート、各種絶縁コーティング、α線遮蔽膜
、クロス含浸及び接着剤等多方面にわたり使用され優れ
た特性を発揮している。In particular, in the fields of electrical and electronic materials, it is used in a wide variety of fields, including enamel wire coatings, films for copper-clad printed circuit boards, insulating films or sheets, various insulating coatings, alpha-ray shielding films, cloth impregnation, and adhesives. It exhibits excellent characteristics.
然し、かかる特性を有するポリイミド樹脂は、各種硝子
、セラミック及びシリコンウェハー等の基板に対して密
着性が劣るという欠点があり、被覆剤等として使用する
と樹脂本来の特性を発揮出来ない場合がある。However, polyimide resins having such properties have the disadvantage of poor adhesion to substrates such as various glass, ceramic, and silicon wafers, and when used as coating materials, etc., the resins may not be able to exhibit their original properties.
このポリイミド樹脂の密着性を改良する為に、各種硝子
、セラミック及びシリコンウェハー等の基板を予め各種
カップリング剤で処理し、基板上にカンプリング剤層を
設ける方法及びポリアミック酸中間体に各種カップリン
グ剤を混合したり、末端に置換シリル基を有するポリア
ミック酸中間体を合成して使用する方法等が知られてい
る。In order to improve the adhesion of this polyimide resin, various types of glass, ceramic, silicon wafer, etc. substrates are treated in advance with various coupling agents, and a coupling agent layer is formed on the substrate. Methods such as mixing a ring agent or synthesizing and using a polyamic acid intermediate having a substituted silyl group at the terminal are known.
ポリイミド樹脂の密着性の改良については、例えば高分
子、３３＠、１１月号、８３０頁、１９８４年及びイン
ターナショナル、ジャーナル、オブ、ポリメリック、マ
テリアルズ（Ｔｎｔｅｒ−ｎａｔｉｏｎａｌ Ｊｏｕｒ
ｎａｌ ｏｆ Ｐｏｌｙｍｅｒｉｃ Ｍａｔｅｒｉａｌ
ｓ ）９巻、２２５真、１９８２年等が知られている。Regarding the improvement of the adhesion of polyimide resins, see, for example, Kobunshi, 33@, November issue, p. 830, 1984, and International, Journal, of Polymeric, Materials.
nal of Polymeric Material
s) Volume 9, 225 Shin, 1982, etc. are known.
（ハ）発明が解決しようとする問題点
上述の高分子、３３巻、１１月号、８３０頁、１９８４
年における基板を各種カップリング剤で処理し基板上に
カップリング剤層を設ける方法は、工程が煩雑となる。(c) Problems to be solved by the invention The above-mentioned polymer, volume 33, November issue, page 830, 1984
The current method of treating a substrate with various coupling agents to form a coupling agent layer on the substrate requires complicated steps.
又、ポリアミック酸中間体溶液中にアミン系シランカッ
プリング剤を添加する方法は、密着性は改良されるもの
のポリアミック酸中間体溶液の粘度低下が大きく保存安
定性が問題となる。Further, although the method of adding an amine-based silane coupling agent to the polyamic acid intermediate solution improves the adhesion, the viscosity of the polyamic acid intermediate solution decreases significantly, resulting in storage stability problems.
更に、高分子、３３巻、１１月号、８３０頁、１９８４
年及びインターナショナル、ジャーナル、オブ、ポリメ
リック、マテリアルズ（Ｉｎｔｅｒｎａｔｉｏ−ｎａｌ
Ｊｏｕｒｎａｌ ｏｆ Ｐｏｌｙｍｅｒｉｃ Ｍａｔ
ｅｒｉａｌｓ） ９巻−２２５頁、１９８２年における
末端に置換シリル基を有するポリアミック酸中間体を合
成して使用する方法は、使用されたシラン力・ノブリン
グ剤は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、ｒ−（ｐ−アミノフェニル）プロ
ピルトリエトキシシラン、γ−アミノプロピルトリメト
キシシラン等のアミノシラン系カンプリング剤のみであ
る。Furthermore, Kobunshi, Vol. 33, November issue, p. 830, 1984
Year and International,Journal of Polymeric,Materials.
Journal of Polymeric Mat
9-225, 1982, the method for synthesizing and using a polyamic acid intermediate having a substituted silyl group at the end is based on the method in which the silane force and knobling agent used are N-β-(aminoethyl)-γ. - Aminosilane camping agents such as -aminopropyltrimethoxysilane, r-(p-aminophenyl)propyltriethoxysilane, and γ-aminopropyltrimethoxysilane.
従って、構造式（１）の４位に各種シリル基を有する１
、２，３．６−テトラヒドロ無水フタル酸をポリイミド
樹脂の各種基板に対する密着性改良に使用するいかなる
方法も知られていない。Therefore, 1 having various silyl groups at the 4-position of structural formula (1)
, 2,3,6-tetrahydrophthalic anhydride is not known to be used to improve the adhesion of polyimide resins to various substrates.
（ニ）問題点を解決するための手段
本発明者らは、ポリイミド樹脂が各種硝子、セラミック
及びシリコンウェハー等の基板に対して密着性が劣ると
いう欠点を解決すべく鋭意努力検討の結果、本発明を完
成するに至ったものである。(d) Means for Solving the Problems The present inventors have made extensive efforts to solve the problem of poor adhesion of polyimide resins to substrates such as various glass, ceramic, and silicon wafers, and have developed the present invention. This led to the completion of the invention.
即ち、本発明はジアミン、テトラカルボン酸２無水物及
び構造式（１）の
Ｒ。That is, the present invention provides a diamine, a tetracarboxylic dianhydride, and R of structural formula (1).
（Ｒ＋ 、Ｒ２、Ｒ３は低級アルキル基で、互いに同じ
であっても異なっていても良い。）４位に各種シリル基
を有する１、２，３．６−テトラヒドロ無水フタル酸か
ら得られる珪素含有ポリイミド樹脂及びその製造法に関
するものである。(R+, R2, and R3 are lower alkyl groups, which may be the same or different.) Silicon-containing material obtained from 1,2,3.6-tetrahydrophthalic anhydride having various silyl groups at the 4-position This invention relates to polyimide resin and its manufacturing method.
本発明のジアミンの具体例としては、ｐ−フェニレンジ
アミン、ｍ−フェニレンジアミン、ジ。Specific examples of the diamine of the present invention include p-phenylenediamine, m-phenylenediamine, and diamine.
アミノジフェニルメタン、ジアミノシフ主ニルエーテル
、２，２−ジアミノジフェニルプロパン、ジアミノジフ
ェニルスルホン、ジアミノベンゾフェノン、ジアミノナ
フタレン、１．３−ビス（４−アミノフェノキシ）ベン
ゼン、１．４−ビス（４−アミノフェノキシ）ベンゼン
、４．４’−ジ（４−アミノフェノキシ）ジフェニルス
ルホン及び２．２′−ビスＣ４−（４−アミノフェノキ
シ）フェニル〕プロパン等の芳香族ジアミンが挙げられ
る。Aminodiphenylmethane, diaminosifhenyl ether, 2,2-diaminodiphenylpropane, diaminodiphenylsulfone, diaminobenzophenone, diaminonaphthalene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene , 4,4'-di(4-aminophenoxy)diphenylsulfone, and 2,2'-bisC4-(4-aminophenoxy)phenyl]propane.
その他目的に応じ、脂環式ジアミン及び脂肪族ジアミン
を使用しても良い。Depending on the purpose, alicyclic diamines and aliphatic diamines may also be used.
又、本発明のテトラカルボン酸２無水物の具体例として
はピロメリット酸２無水物、ヘンシフエノンテトラカル
ボン酸２無水物及びビフェニルテトラカルボン酸２無水
物等の芳香族テトラカルボン酸２無水物、シクロブタン
テトラカルボン酸２無水物、シクロペンタンテトラカル
ボン酸２無水物及びシクロヘキサンテトラカルボン酸２
無水物等の脂環式テトラカルボン酸２無水物、ブタンテ
トラカルボン酸２無水物等の脂肪族テトラカルボン酸２
無水物等が挙げられる。Further, specific examples of the tetracarboxylic dianhydride of the present invention include aromatic tetracarboxylic dianhydrides such as pyromellitic dianhydride, hensiphenonetetracarboxylic dianhydride, and biphenyltetracarboxylic dianhydride. , cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, and cyclohexanetetracarboxylic dianhydride
Alicyclic tetracarboxylic acid dianhydride such as anhydride, aliphatic tetracarboxylic acid dianhydride such as butanetetracarboxylic acid dianhydride
Examples include anhydrides.
又、これらテトラカルボン酸２無水物は１種であっても
２種以上混合して使用しても良い。Further, these tetracarboxylic dianhydrides may be used alone or in combination of two or more.
構造式〔■〕の４位に各種シリル基を有するｌ。l having various silyl groups at the 4-position of the structural formula [■].
２．３．６−テトラヒドロ無水フタル酸の具体例として
は、４−（トリメトキシ）シリル−１，２゜３．６−テ
トラヒドロ無水フタル酸、４−（トリエトキシ）シリル
−１，２，３，６−テトラヒドロ無水フタル酸、４−（
トリプロポキシ）シリル−１，２，３，６−テトラヒド
ロ無水フタル酸及び４− （トリブトキシ）シリル−１
，２，３，６−テトラヒドロ無水フタル酸等を挙げる事
が出来る。゛
又、構造式（Ｉ）の化合物は、例えば特願昭５９−１９
９８５５号の方法等により製造する事が出来る。2.3. Specific examples of 6-tetrahydrophthalic anhydride include 4-(trimethoxy)silyl-1,2゜3.6-tetrahydrophthalic anhydride, 4-(triethoxy)silyl-1,2,3,6 -tetrahydrophthalic anhydride, 4-(
tripropoxy)silyl-1,2,3,6-tetrahydrophthalic anhydride and 4-(tributoxy)silyl-1
, 2,3,6-tetrahydrophthalic anhydride and the like. Furthermore, the compound of structural formula (I) is disclosed in Japanese Patent Application No. 59-19
It can be manufactured by the method of No. 9855, etc.
本発明におけるジアミン、テトラカルボン酸２無水物及
び構造式〔Ｉ〕の４位に各種シリル基を有する１、２．
３．６−テトラヒドロ無水フタル酸は、ジアミン８モル
、テトラカルボン酸２無水物ｂモル及び構造式〔Ｉ〕の
化合物Ｃモルを、次式の関係で
ａ＞ｂ≧ａ／２．２ Ｃａ−ｂ）≧ｃ＞Ｑ反応、重合
する必要がある。Diamine in the present invention, tetracarboxylic dianhydride, and 1, 2. having various silyl groups at the 4-position of structural formula [I].
3.6-Tetrahydrophthalic anhydride is prepared by combining 8 moles of diamine, b moles of tetracarboxylic dianhydride, and C moles of the compound of structural formula [I] according to the relationship of the following formula: a>b≧a/2.2 Ca- b) ≧c>Q reaction, it is necessary to polymerize.
又、ジアミン８モル、テトラカルボン酸２無水物ｂモル
及び構造式（Ｔ）の４位に各種シリル基を有する１、２
，３．６−テトラヒドロ無水フタル酸Ｃモルを、次式の
関係で
ａ＞ｂ≧ａ／２．２（ａ−ｔ））≧ＣＯＯ反応させ、ポ
リアミック酸中間体とした後該中間体を脱水閉環重合す
る事も出来る。In addition, 8 mol of diamine, b mol of tetracarboxylic dianhydride, and 1, 2 having various silyl groups at the 4-position of the structural formula (T).
, 3.6-Tetrahydrophthalic anhydride C moles are reacted with a>b≧a/2.2(at))≧COO according to the following formula to form a polyamic acid intermediate, and then the intermediate is dehydrated. Ring-closing polymerization is also possible.
ここで、ａ≦ｂでは、構造式〔Ｉ〕の４位に各種シリル
基を有する１、２．３．６−テトラヒドロ無水フタル酸
の反応、重合が充分でなく、従って生成する珪素含有ポ
リイミド樹脂の各種基板に対する密着性が充分ではない
。Here, if a≦b, the reaction and polymerization of 1,2,3,6-tetrahydrophthalic anhydride having various silyl groups at the 4-position of structural formula [I] will not be sufficient, and therefore the silicon-containing polyimide resin will be produced. Adhesion to various substrates is not sufficient.
又、ｂ＜ａ／２では、珪素含有ポリイミド樹脂の重合度
が上昇しない。Further, when b<a/2, the degree of polymerization of the silicon-containing polyimide resin does not increase.
更に、２（ａ−ｂ）＜Ｃでは、未反応の構造式（１）の
４位に各種シリル基を有するｌ、２，３゜６−テトラヒ
ドロ無水フタル酸が上記ポリアミック酸中間体の安定性
を阻害する。Furthermore, when 2(a-b)<C, l,2,3゜6-tetrahydrophthalic anhydride having various silyl groups at the 4-position of the unreacted structural formula (1) increases the stability of the polyamic acid intermediate. inhibit.
ジアミン、テトラカルボン酸２無水物及び構造式〔同の
４位に各種シリル基を有する１、２゜３．６−テトラヒ
ドロ無水フタル酸の反応方法は特に限定する必要はない
。There is no need to particularly limit the reaction method of diamine, tetracarboxylic dianhydride, and 1,2°3,6-tetrahydrophthalic anhydride having various silyl groups at the 4-position of the structural formula.
一般に、ジアミンとテトラカルボン酸２無水物を反応後
、構造式（１）で表される４位に各種シリル基を有する
ｌ、２，３．６−テトラヒドロ無水フタル酸を反応、重
合させたり、これら三成分を同時に反応、重合させる方
法が採用される。Generally, after reacting diamine and tetracarboxylic dianhydride, l,2,3.6-tetrahydrophthalic anhydride having various silyl groups at the 4-position represented by structural formula (1) is reacted and polymerized, A method is adopted in which these three components are simultaneously reacted and polymerized.
更に、ジアミン、テトラカルボン酸２無水物及び構造式
（１）の４位に各種シリル基を有する１゜２．３．６−
テトラヒドロ無水フタル酸を反応後、ポリイミド樹脂と
する方法は、コーティング、成形及び含浸等ポリイミド
樹脂の用途により異なるが、−ｉには加工面の容易さか
ら、ジアミン、テトラカルボン酸２無水物及び構造式（
１）の４位に各種シリル基を有する１、２．３．６−テ
トラヒドロ無水フタル酸を反応し、ポリアミック酸中間
体とした後、該中間体を脱水閉環する方法が望ましい。Furthermore, diamine, tetracarboxylic dianhydride, and 1゜2.3.6- having various silyl groups at the 4-position of structural formula (1).
The method of making polyimide resin after reacting tetrahydrophthalic anhydride varies depending on the use of the polyimide resin, such as coating, molding, and impregnation. formula(
A preferred method is to react 1,2,3,6-tetrahydrophthalic anhydride having various silyl groups at the 4-position of 1) to form a polyamic acid intermediate, and then dehydrate and ring-close the intermediate.
この場合、生成するポリアミック酸中間体を単離せずに
ポリイミド樹脂とする１段法或いは生成するポリアミッ
ク酸中間体を単離し、次いで脱水閉環重合してポリイミ
ド樹脂とする２段法いずれの方法も採用出来る。In this case, either a one-step method in which the produced polyamic acid intermediate is made into a polyimide resin without isolating it, or a two-step method in which the produced polyamic acid intermediate is isolated and then subjected to dehydration ring-closing polymerization to produce a polyimide resin can be adopted. I can do it.
又、ポリアミック酸中間体の重合方法としては、通常は
溶液法が好適である。Further, as a method for polymerizing the polyamic acid intermediate, a solution method is usually suitable.
゛溶液重合法に使用される溶剤の具体例としては、Ｎ、
Ｎ−ジメチルホルムアミド、Ｎ、Ｎ−ジメチルアセトア
ミド、Ｎ−メチルピロリドン、Ｎ−メチルカプロラクタ
ム、ジメチルスルホキシド、テトラメチル尿素、ピリジ
ン、ジメチルスルホン、ヘキサメチルホスホルアミド及
びブチロラクトン等を挙げる事が出来る。これらは単独
でも、又混合して使用しても良い。゛Specific examples of solvents used in the solution polymerization method include N,
N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylphosphoramide and butyrolactone can be mentioned. These may be used alone or in combination.
更に、ポリアミック酸中間体を溶解しない溶剤であって
も、その溶剤をポリアミック酸中間体の均一溶液が得ら
れる範囲内で上記溶剤に加えて使用しても良い。Furthermore, even if the solvent does not dissolve the polyamic acid intermediate, it may be used in addition to the above-mentioned solvent within the range where a homogeneous solution of the polyamic acid intermediate can be obtained.
ジアミン、テトラカルボン酸２無水物及び構造式（１）
で表される４位に各種シリル基を有する１、２．３．６
−テトラヒドロ無水フタル酸の反応、重合温度は一２０
〜４００°Ｃの任意の温度を採用出来るが、特に−５〜
３５０°Ｃの範囲が望ましい。Diamine, tetracarboxylic dianhydride and structural formula (1)
1, 2.3.6 having various silyl groups at the 4-position represented by
-Reaction of tetrahydrophthalic anhydride, polymerization temperature is -20
Any temperature between ~400°C can be adopted, but especially -5~
A range of 350°C is desirable.
又、ポリアミック酸中間体生成のための反応温度は一２
０〜１５０℃の任意の温度を選択出来るが、特に−５〜
１００°Ｃの範囲が好ましい。In addition, the reaction temperature for producing polyamic acid intermediate is -2
Any temperature from 0 to 150°C can be selected, especially from -5 to 150°C.
A range of 100°C is preferred.
更にポリアミック酸中間体をポリイミド樹脂に転化する
には、通常は加熱により脱水閉環する方法が採用される
。この加熱脱水閉環温度は、１５０〜４００℃、好まし
くは１７０〜３５０ ’Ｃの任意の温度を選択出来る。Furthermore, in order to convert the polyamic acid intermediate into a polyimide resin, a method of dehydration and ring closure by heating is usually employed. The thermal dehydration ring-closing temperature can be selected from any temperature from 150 to 400°C, preferably from 170 to 350'C.
又この脱水閉環に要する時間は、上記反応温度にもよる
が３０秒〜１０時間、好ましくは５分〜５時間が適当で
ある。The time required for this dehydration ring closure is suitably 30 seconds to 10 hours, preferably 5 minutes to 5 hours, although it depends on the reaction temperature.
ポリアミック酸中間体をポリイミド樹脂に転化する他の
方法として、公知の脱水閉環触媒を使用して化学的に閉
環する事も出来る。As another method for converting a polyamic acid intermediate into a polyimide resin, chemical ring closure can also be performed using a known dehydration ring closure catalyst.
本発明のポリアミッ酸中間体溶液は、各種硝子、セラミ
ック及びシリコンウェハー等の基板に公知の方法で塗布
又は印刷し、一般的に使用される公知の方法でポリイミ
ド樹脂に転化し、基板上に珪素含有ポリイミド樹脂被膜
を形成する事が出来る。The polyamic acid intermediate solution of the present invention is coated or printed on substrates such as various glass, ceramic, and silicon wafers by a known method, and is converted into a polyimide resin by a commonly used known method. A containing polyimide resin film can be formed.
（ホ）発明の効果
本発明のジアミン、テトラカルボン酸２無水物及び構造
式〔■〕の４位に各種シリル基を有する１、２，３．６
−テトラヒドロ無水フタル酸から得られる珪素含有ポリ
イミド樹脂の各種基板に対する密着性は、構造式〔Ｉ〕
の４位に各種シリル基を有する１、２，３．６−テトラ
ヒドロ無水フタル酸を添加しないポリイミド樹脂に比較
して著しく向上する。(e) Effect of the invention The diamine of the invention, tetracarboxylic dianhydride, and 1, 2, 3.6 having various silyl groups at the 4-position of the structural formula [■]
- The adhesion of the silicon-containing polyimide resin obtained from tetrahydrophthalic anhydride to various substrates is determined by the structural formula [I]
This is markedly improved compared to polyimide resins to which 1,2,3,6-tetrahydrophthalic anhydride having various silyl groups at the 4-position is not added.
又、本発明のポリアミック酸中間体溶液を各種硝子、セ
ラミック及びシリコンウェハー等の基板に塗布又は印刷
後、ポリイミド樹脂に転化し被覆する場合には、基板を
カップリング剤処理等の下地処理を行う事なくして基板
と強固に密着し、これらポリイミド樹脂本来の特性を発
揮する事が出来る。In addition, when the polyamic acid intermediate solution of the present invention is coated or printed on various types of glass, ceramic, silicon wafer, etc. substrates, and then converted into polyimide resin and coated, the substrate is subjected to surface treatment such as coupling agent treatment. It is possible to firmly adhere to the substrate without any problems and exhibit the original characteristics of these polyimide resins.
（へ）実施例
吹に実施例を挙げて本発明の詳細な説明するが、本発明
はこれらに限定されるものではない実施例１
ンアミノジフェニルエーテル１０．０１ｇ（０，０５モ
ル）をＮ−メチル２−ピロリドン１５０ｍＡに加え撹拌
して均一溶液とした後、ヘンシフエノンテトラカルボン
酸２無水物１５゜３１ ｇ （０，０４７５モル）を加
え１時間攪拌を続け、更に、４−（トリメトキシ）シリ
ル−１，２，３，６−テトラヒドロ無水フタル酸１゜３
６ｇ （０，００５モル）を加え、一時間攪拌を続け、
ポリアミック酸組成物溶液を調製した。(f) Examples The present invention will be explained in detail by referring to Examples, but the present invention is not limited thereto. After adding 150 mA of methyl 2-pyrrolidone and stirring to make a homogeneous solution, 15.31 g (0,0475 mol) of hensifhenonetetracarboxylic dianhydride was added and stirring was continued for 1 hour, and then 4-(trimethoxy) Silyl-1,2,3,6-tetrahydrophthalic anhydride 1°3
Add 6g (0,005 mol) and continue stirring for 1 hour.
A polyamic acid composition solution was prepared.
得られたポリアミック酸組成物溶液の還元粘度η８，７
Ｃは０．５２ ｄ Ｎ／ｇ （３０’Ｃ）であった。Reduced viscosity of the obtained polyamic acid composition solution η8,7
C was 0.52 dN/g (30'C).
このポリアミック酸組成物溶液を硝子板上にスピナーを
使用して塗布し、２５０°Ｃで１時間加熱してポリイミ
ド樹脂被膜を形成した。This polyamic acid composition solution was applied onto a glass plate using a spinner and heated at 250°C for 1 hour to form a polyimide resin coating.
生成ポリイミド樹脂の赤外吸収スペクトル及び螢光Ｘ線
の測定結果より、珪素原子を０．４重量％含有したポリ
イミド樹脂である事を確認した。From the infrared absorption spectrum and fluorescent X-ray measurement results of the polyimide resin produced, it was confirmed that the polyimide resin contained 0.4% by weight of silicon atoms.
又、このポリイミド樹脂被膜を形成した硝子板を沸騰水
中で１時間煮沸したところ、ポリイミド樹脂被膜の剥離
は全く認められず、ポリイミド樹脂被膜は硝子に強固に
密着していた。Further, when the glass plate on which this polyimide resin coating was formed was boiled in boiling water for 1 hour, no peeling of the polyimide resin coating was observed, and the polyimide resin coating was firmly adhered to the glass.
尚、このポリイミド樹脂の赤外線吸収スペクトルを図１
に示す。The infrared absorption spectrum of this polyimide resin is shown in Figure 1.
Shown below.
比較例１
４− （トリメトキシ）シリル−１，２，３，６−テト
ラヒドロ無水フタル酸を加えない他は、実施例１と同様
にしてポリアミック酸組成物溶液を調製後、硝子基板上
にポリイミド樹脂被膜を形成した。Comparative Example 1 After preparing a polyamic acid composition solution in the same manner as in Example 1 except that 4-(trimethoxy)silyl-1,2,3,6-tetrahydrophthalic anhydride was not added, a polyimide resin was placed on a glass substrate. A film was formed.
このポリイミド樹脂被膜を形成した硝子板を沸駿水中で
１時間煮沸したところ、ポリイミド樹脂被膜は硝子板よ
り完全にＭ’ｌ ｆｒ’ｆｂ シてしまった。When the glass plate on which the polyimide resin coating was formed was boiled in boiling water for 1 hour, the polyimide resin coating completely disappeared from the glass plate.
図１は、実施例１の赤外線吸収スペクトルを示し縦軸は
透過率（％）、横軸は波数Ｃ「“である。FIG. 1 shows the infrared absorption spectrum of Example 1, with the vertical axis representing the transmittance (%) and the horizontal axis representing the wave number C.
Claims (1)
I 〕で表される ▲数式、化学式、表等があります▼〔 I 〕 （Ｒ＿１、Ｒ＿２、Ｒ＿３は低級アルキル基で、互いに
同じであっても異なっていても良い。）４位に各種シリ
ル基を有する１，２，３，６−テトラヒドロ無水フタル
酸から得られる珪素含有ポリイミド樹脂。 ２、ジアミンａモル、テトラカルボン酸２無水物ｂモル
及び構造式〔 I 〕で表される４位に各種シリル基を有
する１，２，３，６−テトラヒドロ無水フタル酸ｃモル
を、次式の関係ａ＞ｂ≧ａ／２、２（ａ−ｂ）≧ｃ＞０ 反応、重合させる事を特徴とする珪素含有ポリイミド樹
脂の製造法。 ３、ジアミンａモル、テトラカルボン酸２無水物ｂモル
及び構造式〔 I 〕で表される４位に各種シリル基を有
する１，２，３，６−テトラヒドロ無水フタル酸ｃモル
を、次式の関係で ａ＞ｂ≧ａ／２、２（ａ−ｂ）≧ｃ＞０ 反応させ、ポリアミック酸中間体とした後該中間体を脱
水閉環する事を特徴とする珪素含有ポリイミド樹脂の製
造法。[Claims] 1. Diamine, tetracarboxylic dianhydride, and structural formula [
There are ▲mathematical formulas, chemical formulas, tables, etc. represented by 〔I〕. A silicon-containing polyimide resin obtained from 1,2,3,6-tetrahydrophthalic anhydride having 2. A mol of diamine, b mol of tetracarboxylic dianhydride, and c mol of 1,2,3,6-tetrahydrophthalic anhydride having various silyl groups at the 4-position represented by the structural formula [I] are combined into the following formula: A method for producing a silicon-containing polyimide resin characterized by reaction and polymerization in the following relationships: a>b≧a/2, 2(a-b)≧c>0. 3. A mole of diamine, b mole of tetracarboxylic dianhydride, and c mole of 1,2,3,6-tetrahydrophthalic anhydride having various silyl groups at the 4-position represented by the structural formula [I], were added by the following formula: a>b≧a/2, 2(a-b)≧c>0 A method for producing a silicon-containing polyimide resin characterized by reacting to form a polyamic acid intermediate and then dehydrating and ring-closing the intermediate. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16265985A JPS6222830A (en) | 1985-07-23 | 1985-07-23 | Silicon-containing polyimide resin and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16265985A JPS6222830A (en) | 1985-07-23 | 1985-07-23 | Silicon-containing polyimide resin and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6222830A true JPS6222830A (en) | 1987-01-31 |
| JPH0211616B2 JPH0211616B2 (en) | 1990-03-15 |
Family
ID=15758834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16265985A Granted JPS6222830A (en) | 1985-07-23 | 1985-07-23 | Silicon-containing polyimide resin and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6222830A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0491130A (en) * | 1990-08-06 | 1992-03-24 | Shin Etsu Chem Co Ltd | Curable resin solution composition, production thereof and protecting film for electronic part |
| JPH0489827A (en) * | 1990-08-03 | 1992-03-24 | Shin Etsu Chem Co Ltd | Polyamic acid copolymer and its preparation |
| JPH04351667A (en) * | 1991-05-29 | 1992-12-07 | Shin Etsu Chem Co Ltd | Curable resin composition and protective film for electronic component |
| US5262505A (en) * | 1991-07-30 | 1993-11-16 | Dow Corning Toray Silicone Co. Ltd. | Silicone modified polyimide resin and method for preparing same |
| WO2006118353A1 (en) * | 2005-05-02 | 2006-11-09 | Soken Chemical & Engineering Co., Ltd. | Resin composition excellent in heat resistance and adhesiveness, and method for producing same |
| US12068108B2 (en) | 2018-12-10 | 2024-08-20 | Panasonic Intellectual Property Management Co., Ltd. | Electrochemical device electrode and electrochemical device |
-
1985
- 1985-07-23 JP JP16265985A patent/JPS6222830A/en active Granted
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0489827A (en) * | 1990-08-03 | 1992-03-24 | Shin Etsu Chem Co Ltd | Polyamic acid copolymer and its preparation |
| JPH0491130A (en) * | 1990-08-06 | 1992-03-24 | Shin Etsu Chem Co Ltd | Curable resin solution composition, production thereof and protecting film for electronic part |
| JPH04351667A (en) * | 1991-05-29 | 1992-12-07 | Shin Etsu Chem Co Ltd | Curable resin composition and protective film for electronic component |
| US5262505A (en) * | 1991-07-30 | 1993-11-16 | Dow Corning Toray Silicone Co. Ltd. | Silicone modified polyimide resin and method for preparing same |
| WO2006118353A1 (en) * | 2005-05-02 | 2006-11-09 | Soken Chemical & Engineering Co., Ltd. | Resin composition excellent in heat resistance and adhesiveness, and method for producing same |
| JP5119493B2 (en) * | 2005-05-02 | 2013-01-16 | 綜研化学株式会社 | Resin composition excellent in heat resistance and adhesiveness and method for producing the same |
| US12068108B2 (en) | 2018-12-10 | 2024-08-20 | Panasonic Intellectual Property Management Co., Ltd. | Electrochemical device electrode and electrochemical device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0211616B2 (en) | 1990-03-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |