JPH0489492A - Acid ahydride group-containing disiloxane and its production - Google Patents
Acid ahydride group-containing disiloxane and its productionInfo
- Publication number
- JPH0489492A JPH0489492A JP20076090A JP20076090A JPH0489492A JP H0489492 A JPH0489492 A JP H0489492A JP 20076090 A JP20076090 A JP 20076090A JP 20076090 A JP20076090 A JP 20076090A JP H0489492 A JPH0489492 A JP H0489492A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- group
- containing disiloxane
- disiloxane
- acid anhydride
- 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.)
- Granted
Links
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000002253 acid Substances 0.000 title 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 6
- 125000004018 acid anhydride group Chemical group 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 229920001721 polyimide Polymers 0.000 abstract description 12
- 239000009719 polyimide resin Substances 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 5
- 229920002545 silicone oil Polymers 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 229930195733 hydrocarbon Natural products 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- -1 glass Chemical compound 0.000 description 5
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- OFPHSIZCXNVOCM-UHFFFAOYSA-N 3-[[(2,3-dicarboxyphenyl)-dimethylsilyl]oxy-dimethylsilyl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1[Si](C)(C)O[Si](C)(C)C1=CC=CC(C(O)=O)=C1C(O)=O OFPHSIZCXNVOCM-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)C1=CC=C(N)C=C1 ZYEDGEXYGKWJPB-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- 241000219495 Betulaceae Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、無機物への接着性に優れていると共に、成形
性、加工性などが改善されたシリコーン変性ポリイミド
樹脂の原料、両末端に酸無水物基を含有し、各種樹脂の
改質剤として用いられるシリコーンオイルの原料などと
して有用な下記一般式（Ｉ）
（但し、式中Ｒ，Ｒ’は互いに同−又は異種の一価炭化
水素基、ｍは０〜３の整数である。）（但し、式中Ｒ，
Ｒ’は互いに同−又は異種の一価炭化水素基、ｍはＯ〜
３の整数である。）で示される新規な酸無水物基含有ジ
シロキサン及びその製造方法に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention is a raw material for a silicone-modified polyimide resin that has excellent adhesion to inorganic materials and improved moldability, processability, etc. The following general formula (I) contains an anhydride group and is useful as a raw material for silicone oil used as a modifier for various resins. (However, in the formula, R and R' are monovalent hydrocarbons of the same or different types. group, m is an integer of 0 to 3.) (However, in the formula, R,
R' is the same or different monovalent hydrocarbon group, m is O~
It is an integer of 3. ) and a method for producing the same.
〔従来の技術及び発明が解決しようとする課題〕ポリイ
ミド樹脂は一般的特徴として優れた耐熱性、耐燃性、電
気・機械的特性などを有するため、銅張積層板、多層プ
リント配線板用材料などの複合材料として多用され、Ｌ
ＳＩの多層配線用パッシベーション膜、メモリー素子用
α線遮断膜、磁気ヘッドなどの多層配線絶縁膜、液晶配
向膜などにワニスとして、フレキシブルプリント配線板
基板などにフィルムとして利用でき、近年の産業上非常
に有用な樹脂である。しかし、ポリイミド樹脂にはケイ
素や銅といった金属及びガラスなどの無機物との自己接
着性に欠けていること、また、高沸点の極性溶媒にのみ
溶解性が限定されかつワニス粘度が高いこと、ならびに
硬化物の融点が高いことのために成形性及び加工性に欠
けているなどの欠点があり、より多くの用途に使用する
ためには種々の物性の改善が常々望まれていた。[Prior art and problems to be solved by the invention] Polyimide resin generally has excellent heat resistance, flame resistance, electrical and mechanical properties, etc., so it is used as a material for copper-clad laminates, multilayer printed wiring boards, etc. It is widely used as a composite material for L
It can be used as a varnish for SI multilayer wiring passivation films, alpha ray blocking films for memory devices, multilayer wiring insulation films for magnetic heads, liquid crystal alignment films, etc., and as a film for flexible printed wiring board substrates, etc., and has become extremely popular in industry in recent years. It is a useful resin for However, polyimide resin lacks self-adhesiveness with metals such as silicon and copper and inorganic materials such as glass, has limited solubility only in high-boiling polar solvents, has high varnish viscosity, and hardens. Due to its high melting point, it has drawbacks such as poor moldability and processability, and it has always been desired to improve its various physical properties in order to use it in more applications.
〔課題を解決するための手段及び作用〕本発明者は上記
要望に応えるべく鋭意検討を重ねた結果、下記一般式（
ＩＩ）
（但し、式中Ｒ，Ｒ’は互いに同−又は異種の一価炭化
水素基１ｍはＯ〜３の整数である。）で示されるシクロ
ペンタジェニルアルキル基含有ジシロキサンと無水マレ
イン酸とを反応させることにより、下記一般式（Ｉ）
（但し、式中Ｒ，Ｒ’及びｍは上記と同様の意味を示す
。）
で示される新規な酸無水物基含有ジシロキサンが得られ
ると共に、該ジシロキサンが上述したポリイミド樹脂の
各種欠点を改善し、かつ新規な特性を有するシリコーン
変性ポリイミド樹脂を与え得るものであるほか、種々の
用途に使用し得るものであることを見い出した。[Means and effects for solving the problem] As a result of intensive studies in order to meet the above-mentioned demands, the present inventor has developed the following general formula (
II) (However, in the formula, R and R' are the same or different monovalent hydrocarbon groups 1m is an integer of O to 3.) A cyclopentagenylalkyl group-containing disiloxane and maleic anhydride By reacting with It has been discovered that the disiloxane can improve the various drawbacks of polyimide resins mentioned above, provide silicone-modified polyimide resins with novel properties, and can also be used for various purposes.
即ち、上記式（Ｉ）で示される酸無水物基含有ジシロキ
サンは、これを用いてポリイミド樹脂骨格中にシロキサ
ン結合を導入することにより、無機物への自己接着性を
大幅に向上させることができ、また、有機溶剤への溶解
性が向上するため、低粘度で高濃度のワニスを得ること
が可能となる上、硬化物のガラス転移点が下がるため、
加熱成形が可能となるなど、ポリイミド樹脂の成形性及
び加工性を向上させることができるものである。That is, the acid anhydride group-containing disiloxane represented by the above formula (I) can significantly improve self-adhesion to inorganic materials by introducing siloxane bonds into the polyimide resin skeleton. In addition, because the solubility in organic solvents is improved, it is possible to obtain a varnish with low viscosity and high concentration, and the glass transition point of the cured product is lowered.
It is possible to improve the moldability and processability of polyimide resin, such as by enabling heat molding.
また、該酸無水物基含有ジシロキサンは新規な両末端変
性シリコーンオイルの原料として有用であり、環状シロ
キサン、例えばオクタメチルシクロテトラシロキサンと
酸触媒、例えば硫酸の存在下で平衡化させることにより
、両末端に酸無水物基を含有する高分子量のシリコーン
オイルを得ることができ、このものは各種樹脂の改質剤
として有効に用いられる。In addition, the acid anhydride group-containing disiloxane is useful as a raw material for a new double-end modified silicone oil, and by equilibrating it with a cyclic siloxane, such as octamethylcyclotetrasiloxane, in the presence of an acid catalyst, such as sulfuric acid, A high molecular weight silicone oil containing acid anhydride groups at both ends can be obtained, and this oil can be effectively used as a modifier for various resins.
なお、従来より酸無水物基含有ジシロキサンとしては、
１，３−ビス（ジカルボキシフェニル）−１，１，３，
３−テトラメチルジシロキサン２無水物（独国特許第３
５４２３４６号公報）、５．５’−（Ｉ，１，３，３−
テトラメチル−１，３−ジシロキサンジイル）−ビスノ
ルボルナン−２，３−ジカルボン酸無水物（公表特許公
報昭５９−５０５．２０８号）、１．３−ビス（ジカル
ボキシブチル）−１，１゜３．３−テトラメチルジシロ
キサン２無水物（特開昭５７−１２３２２３号公報）、
１．３−ビス（トリメリットオキシプロピル）−１，１
，３，３−テトラメチルジシロキサン２無水物（特開平
１−２５４６３１号公報）が知られているが、一般式（
Ｉ）で示される本発明のジシロキサン化合物は未だ知ら
れていない。In addition, conventional acid anhydride group-containing disiloxanes include:
1,3-bis(dicarboxyphenyl)-1,1,3,
3-tetramethyldisiloxane dianhydride (German patent no.
542346), 5.5'-(I,1,3,3-
Tetramethyl-1,3-disiloxanediyl)-bisnorbornane-2,3-dicarboxylic acid anhydride (Publication Patent Publication No. 59-505.208), 1,3-bis(dicarboxybutyl)-1,1゜3.3-Tetramethyldisiloxane dianhydride (JP-A-57-123223),
1.3-bis(trimellitoxypropyl)-1,1
, 3,3-tetramethyldisiloxane dianhydride (JP-A-1-254631) is known, but it has the general formula (
The disiloxane compound of the present invention represented by I) is not yet known.
従って、本発明は式（Ｉ）で示される酸無水物基含有ジ
シロキサン及び式（Ｉｌ）で示されるシクロペンタジェ
ニルアルキル基含有ジシロキサンと無水マレイン酸とを
反応させることからなる式（Ｉ）で示される酸無水物基
含有ジシロキサンの製造方法を提供する。Therefore, the present invention provides the formula (I) which consists of reacting an acid anhydride group-containing disiloxane represented by the formula (I) and a cyclopentagenylalkyl group-containing disiloxane represented by the formula (Il) with maleic anhydride. ) provides a method for producing an acid anhydride group-containing disiloxane.
以下、本発明について更に詳しく説明する。The present invention will be explained in more detail below.
本発明の酸無水物基含有ジシロキサンは、下記式（Ｉ）
（但し、式中Ｒ，Ｒ’は互いに同−又は異種の一価炭化
水素基、ｍはＯ〜３の整数である。）で示され、ケイ素
原子の各々にそれぞれ一つずつ５−ノルボルネン−２，
３−ジカルボン酸無水物基が直接もしくはアルキレン鎖
を介して結合しているジシロキサンである。The acid anhydride group-containing disiloxane of the present invention has the following formula (I) (wherein R and R' are the same or different monovalent hydrocarbon groups, and m is an integer of O to 3.) 5-norbornene-2, one for each silicon atom,
It is a disiloxane in which a 3-dicarboxylic anhydride group is bonded directly or via an alkylene chain.
ここで、Ｒ，Ｒ’の一価炭化水素基としては、例えばメ
チル基、エチル基、プロピル基等の炭素数１〜６のアル
キル基、炭素数５〜６のシクロアルキル基、フェニル基
等が挙げられるが、中でもメチル基が最も好ましい。こ
の式（Ｉ）で示される酸無水物基含有ジシロキサンを具
体的に示すと、
などを挙げることができる。Here, examples of the monovalent hydrocarbon groups of R and R' include alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, and propyl group, cycloalkyl groups having 5 to 6 carbon atoms, and phenyl groups. Among them, methyl group is the most preferred. Specific examples of the acid anhydride group-containing disiloxane represented by formula (I) include:
本発明の上記式（Ｉ）で示される酸無水物基含有ジシロ
キサンは上述したように無機物への接着性が良好で、成
形性、作業性等が改善された新規なシリコーン変性ポリ
イミド樹脂の原料として有用なものである。この場合有
機ジアミン、例えばＰ−フェニレンジアミン、ｍ−フェ
ニレンジアミン、４．４’−ジアミノジフェニルメタン
、４，４′−ジアミノジフエニルエーテル、２，２′−
ビス（４−アミノフェニル）プロパン、３，３′−ジア
ミノジフェニルスルホン、４，４′−ジアミノジフェニ
ルスルホン、２，２−ビス［４−（４−アミノフェノキ
シ）フェニル〕プロパン、２，２−ビス〔３−メチル−
４−（４−アミノフェノキシ）フェニル〕プロパンなど
の１種又は２種以上と本発明の酸無水物基含有ジシロキ
サンを単独で反応させ、あるいは他の２無水物、例えば
ピロメリット酸二無水物、ベンゾフェノンテトラカルボ
ン酸二無水物、ジフェニルテトラカルボン酸二無水物、
ビス（３゜４−ジカルボキシフェニル）スルホンニ無水
物、２．２−ビス（３，４−ジカルボキシフェニル）プ
ロパンニ無水物、ｐ−ビス（３，４−ジカルボキシフェ
ノキシ）フェニルニ無水物などの１種又は２種以上との
混合物として反応させ、これにより諸特性が改善された
シリコーン変性ポリイミド樹脂を得ることができる。As mentioned above, the acid anhydride group-containing disiloxane represented by the above formula (I) of the present invention is a raw material for a new silicone-modified polyimide resin that has good adhesion to inorganic substances and has improved moldability, workability, etc. It is useful as a. In this case, organic diamines are used, such as P-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2'-
Bis(4-aminophenyl)propane, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis [3-methyl-
The acid anhydride group-containing disiloxane of the present invention is reacted alone with one or more of 4-(4-aminophenoxy)phenyl]propane, or other dianhydrides, such as pyromellitic dianhydride. , benzophenonetetracarboxylic dianhydride, diphenyltetracarboxylic dianhydride,
1 such as bis(3゜4-dicarboxyphenyl)sulfone dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propanihydride, p-bis(3,4-dicarboxyphenoxy)phenyl dianhydride, etc. By reacting as a species or a mixture of two or more species, a silicone-modified polyimide resin with improved various properties can be obtained.
上記式（Ｉ）で示される本発明の酸無水物基含有ジシロ
キサンは、下記−形成（ＩＩ）（但し、式中Ｒ，Ｒ’及
びｍは上記と同様の意味を示す、）
で示されるシクロペンタジェニルアルキル基含有ジシロ
キサンと無水マレイン酸とを使用し、下記に示すような
ディールス°アルダー反応によって、容易に合成するこ
とができる。The acid anhydride group-containing disiloxane of the present invention represented by the above formula (I) is represented by the following -formation (II) (wherein R, R' and m have the same meanings as above) It can be easily synthesized using a cyclopentadienyl alkyl group-containing disiloxane and maleic anhydride by the Diels° Alder reaction as shown below.
二こで、上記式（ＩＩ）で示されるシクロペンタジェニ
ルアルキル基含有ジシロキサンはシクロペンタジエニル
基含有モノアルコキシシランもしくはシクロペンタジェ
ニルアルキル基含有モノアルコキシシランを加水分解縮
合するなどの操作により得ることができる。In this case, the cyclopentadienyl alkyl group-containing disiloxane represented by the above formula (II) can be obtained by hydrolytic condensation of a cyclopentadienyl group-containing monoalkoxysilane or a cyclopentadienyl alkyl group-containing monoalkoxysilane. It can be obtained by
また、上記ディールス・アルダ−反応は無溶媒で十分進
行するが、必要に応してベンゼン、トルエン、０−キシ
レン、ｍ−キシレン、混合キシレン、シクロヘキセン、
エチルエーテル、テトラハイドロフランなどの溶媒を使
用してもよい。この反応は常温でも進行するが、必要に
応じて溶媒の還流温度で反応させても構わない。反応時
間は無水マレイン酸と反応せしめる基質、すなわち上記
−形成（Ｉ［）で示される化合物の種類によって左右さ
れるものであり、約３０分径度から数１０時間程度また
はそれ以上に自由に選定することが可能である。なお、
反応に際してＡＱＣＱ、、ＢＦ、。Although the above Diels-Alder reaction proceeds satisfactorily without a solvent, benzene, toluene, 0-xylene, m-xylene, mixed xylene, cyclohexene,
Solvents such as ethyl ether and tetrahydrofuran may also be used. Although this reaction proceeds at room temperature, it may be carried out at the reflux temperature of the solvent if necessary. The reaction time depends on the type of substrate to be reacted with maleic anhydride, that is, the type of compound represented by -formation (I[) above, and can be freely selected from about 30 minutes to several tens of hours or more. It is possible to do so. In addition,
During the reaction AQCQ,, BF,.
ＳｎＣΩ２などの触媒を使用しても構わない。A catalyst such as SnCΩ2 may also be used.
上記反応において、無水マレイン酸の使用量は一般式（
Ｉｆ）で示されるシクロペンタジェニルアルキル基含有
ジシロキサンに対して、少なくとも２倍モル以上であれ
ば任意の量を選ぶことが可能であるが、経済的な理由か
ら２〜２．２倍モルが特に好ましい。In the above reaction, the amount of maleic anhydride used is determined by the general formula (
Any amount can be selected as long as it is at least 2 times the mole of the cyclopentagenyl alkyl group-containing disiloxane represented by If), but from 2 to 2.2 times the mole for economical reasons. is particularly preferred.
このようにして得られる式（Ｉ）で示される酸無水物基
含有ジシロキサンは再結晶により精製が可能であり、再
結晶溶媒としては塩化メチレン。The acid anhydride group-containing disiloxane represented by the formula (I) thus obtained can be purified by recrystallization, and methylene chloride is used as the recrystallization solvent.
クロロホルムなどの塩素系溶媒とｎ−ヘキサンなどの炭
化水素系溶媒の混合溶媒もしくは氷酢酸と無水酢酸の混
合溶媒などを用いることができる。A mixed solvent of a chlorine-based solvent such as chloroform and a hydrocarbon-based solvent such as n-hexane, or a mixed solvent of glacial acetic acid and acetic anhydride can be used.
以上説明したように、本発明の式（Ｉ）で示される酸無
水物基含有ジシロキサンは、ポリイミド樹脂の原料とし
て有用で、無機物への接着性に優れると共に、成形性、
加工性が改善されたシリコーン変性ポリイミド樹脂を得
ることができ、また各種樹脂の改質剤として有効に用い
られる両末端変性シリコーンオイルの原料などとしても
有用である。また、本発明の製造方法によれば、安価な
無水マレイン酸を原料とし、簡単な工程で確実に式（ｒ
）で示される酸無水物基含有ジシロキサンを製造できる
ものである。As explained above, the acid anhydride group-containing disiloxane represented by the formula (I) of the present invention is useful as a raw material for polyimide resin, has excellent adhesion to inorganic materials, and has excellent moldability and
It is possible to obtain a silicone-modified polyimide resin with improved processability, and it is also useful as a raw material for both-terminally modified silicone oil, which is effectively used as a modifier for various resins. Furthermore, according to the production method of the present invention, inexpensive maleic anhydride is used as a raw material, and formula (r
) can produce an acid anhydride group-containing disiloxane.
以下、実施例を挙げて本発明を具体的に説明するが、本
発明は下記の実施例に制限されるものではない。EXAMPLES Hereinafter, the present invention will be specifically explained with reference to examples, but the present invention is not limited to the following examples.
温度計、撹拌装置、ジムロート冷却器を備えた２００ｄ
のガラス製反応器に無水マレイン酸８．２ｇ （０，０
８３６ｍｏｌ）及びトルエン１００ｒｎ９．を仕込み、
３０〜４０℃で撹拌し、無水マレイン酸を完全に溶解さ
せた。次いで室温まで冷却した後、滴下ロートを用いて
、１，３−ビス（シクロペンタジェニル）−１，１，３
，３−テトラメチルジシロキサン１０ｇ （０，０３８
ｍｏ−１）を徐々に反応器内に導入した。しだいに発熱
が生じ、内温が３０〜４０℃まで上昇すると共に、系内
に白色の結晶が多量に析出した。撹拌を維持しながら１
０時間熟成した後濾過し、白色結晶物をトルエン洗浄後
。200d with thermometer, stirrer and Dimroth cooler
8.2 g of maleic anhydride (0,0
836 mol) and toluene 100rn9. Prepare
The mixture was stirred at 30-40°C to completely dissolve maleic anhydride. Then, after cooling to room temperature, using a dropping funnel, 1,3-bis(cyclopentagenyl)-1,1,3
,3-tetramethyldisiloxane 10g (0,038
m-1) was gradually introduced into the reactor. Heat generation gradually occurred, and the internal temperature rose to 30 to 40°C, and a large amount of white crystals precipitated in the system. 1 while maintaining stirring
After aging for 0 hours, it was filtered and the white crystals were washed with toluene.
真空乾燥した。次いで塩化メチレン／ｎ−ヘキサンから
再結晶した。得られた白色結晶物の融点は１５６〜１５
８℃であった。Vacuum dried. It was then recrystallized from methylene chloride/n-hexane. The melting point of the obtained white crystalline substance is 156-15
The temperature was 8°C.
得られた白色結晶物は核磁気共鳴（ＩＨ−ＮＭＲ）及び
赤外吸収（ＩＲ）より、下記構造式であることを示した
。Nuclear magnetic resonance (IH-NMR) and infrared absorption (IR) showed that the obtained white crystalline substance had the following structural formula.
Claims (1)
水素基、ｍは０〜３の整数である。）で示される酸無水
物基含有ジシロキサン。 ２、下記一般式（II） ▲数式、化学式、表等があります▼…（II） （但し、式中Ｒ、Ｒ’は互いに同一又は異種の一価炭化
水素基、ｍは０〜３の整数である。）で示されるシクロ
ペンタジエニルアルキル基含有ジシロキサンと無水マレ
イン酸とを反応させることを特徴とする請求項１記載の
酸無水物基含有ジシロキサンの製造方法。[Claims] 1. The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (However, in the formula, R and R' are the same or different monovalent hydrocarbon groups, m is an integer of 0 to 3.) An acid anhydride group-containing disiloxane. 2. The following general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (However, in the formula, R and R' are the same or different monovalent hydrocarbon groups, and m is an integer from 0 to 3. 2. The method for producing an acid anhydride group-containing disiloxane according to claim 1, characterized in that the cyclopentadienyl alkyl group-containing disiloxane represented by the following formula is reacted with maleic anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20076090A JP2805999B2 (en) | 1990-07-26 | 1990-07-26 | Acid anhydride group-containing disiloxane and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20076090A JP2805999B2 (en) | 1990-07-26 | 1990-07-26 | Acid anhydride group-containing disiloxane and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0489492A true JPH0489492A (en) | 1992-03-23 |
| JP2805999B2 JP2805999B2 (en) | 1998-09-30 |
Family
ID=16429719
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20076090A Expired - Fee Related JP2805999B2 (en) | 1990-07-26 | 1990-07-26 | Acid anhydride group-containing disiloxane and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2805999B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6455640B2 (en) | 2000-04-25 | 2002-09-24 | Dow Corning Toray Silicone, Co., Ltd. | Method for producing basic amino acid-modified organopolysiloxane |
| EP1921673A2 (en) | 2006-11-10 | 2008-05-14 | Shin-Etsu Chemical Co., Ltd. | Method for manufacturing semiconductor substrate |
-
1990
- 1990-07-26 JP JP20076090A patent/JP2805999B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6455640B2 (en) | 2000-04-25 | 2002-09-24 | Dow Corning Toray Silicone, Co., Ltd. | Method for producing basic amino acid-modified organopolysiloxane |
| EP1921673A2 (en) | 2006-11-10 | 2008-05-14 | Shin-Etsu Chemical Co., Ltd. | Method for manufacturing semiconductor substrate |
| US8263478B2 (en) * | 2006-11-10 | 2012-09-11 | Shin-Etsu Chemical Co., Ltd. | Method for manufacturing semiconductor substrate |
| EP1921673B1 (en) * | 2006-11-10 | 2014-04-30 | Shin-Etsu Chemical Co., Ltd. | Method for manufacturing semiconductor substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2805999B2 (en) | 1998-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6516048B2 (en) | Polyimide precursor and polyimide | |
| EP0113357B1 (en) | Silicone-imide copolymers and method for making | |
| JPH07324133A (en) | Silicate group-containing polyimide | |
| JPH0291125A (en) | Silicone polyimide and preparation thereof | |
| JP2606402B2 (en) | Curable resin and method for producing the same | |
| JP5270865B2 (en) | Adhesive and its use | |
| JP2722915B2 (en) | Curable resin, method for producing the same, and protective film for electronic component | |
| US5258487A (en) | Polyamido-acid copolymer and its manufacture | |
| JPS61159425A (en) | Polyanhydride-siloxane and polyimide-siloxane obtained therefrom | |
| JP2923007B2 (en) | Solvent-soluble polyimide, method for producing the same, and material for color filter | |
| WO2006118353A1 (en) | Resin composition excellent in heat resistance and adhesiveness, and method for producing same | |
| JPH08183856A (en) | Polyimide resin and production thereof | |
| KR100266998B1 (en) | Polyimide silicon resin precursor composition | |
| JPH0489492A (en) | Acid ahydride group-containing disiloxane and its production | |
| US4591653A (en) | Silicone-polyimide precursor and process for producing same | |
| JPH0940777A (en) | Polyimide/siloxane block copolymer, varnish containing it and method of using it | |
| JPH0413724A (en) | Soluble polyimide, it's production and coating liquid for liquid crystal oriented film | |
| JP7388296B2 (en) | Silicon-containing tetracarboxylic dianhydride, its production method and polyimide resin | |
| US5789524A (en) | Chemical imidization reagent for polyimide synthesis | |
| JPH08120075A (en) | Production of copolyimide | |
| KR0163960B1 (en) | Curable resin solution compositions, their preparation and electronic part protective coatings | |
| JP2712993B2 (en) | Curable resin, solution thereof, production method thereof, and protective film for electronic component | |
| JPH09132710A (en) | Polyimide resin composition and its use | |
| JPH04214786A (en) | Production of heat-resistant adhesive | |
| JPS63225629A (en) | Polyimide resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080724 Year of fee payment: 10 |
|
| LAPS | Cancellation because of no payment of annual fees |