JP2021195319A - Silicon-containing tetracarboxylic acid dianhydride, production method thereof, and polyimide resin - Google Patents
Silicon-containing tetracarboxylic acid dianhydride, production method thereof, and polyimide resin Download PDFInfo
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 27
- 239000010703 silicon Substances 0.000 title claims abstract description 26
- -1 tetracarboxylic acid dianhydride Chemical class 0.000 title claims abstract description 23
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 4
- 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 claims description 22
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 22
- 150000008065 acid anhydrides Chemical class 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 abstract description 9
- 230000003287 optical effect Effects 0.000 abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 239000004642 Polyimide Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 229920005575 poly(amic acid) Polymers 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- UHXCHUWSQRLZJS-UHFFFAOYSA-N (4-dimethylsilylidenecyclohexa-2,5-dien-1-ylidene)-dimethylsilane Chemical compound C[Si](C)C1=CC=C([Si](C)C)C=C1 UHXCHUWSQRLZJS-UHFFFAOYSA-N 0.000 description 2
- 0 *C(C(*)(CC1(*)C2C(O3)=O)C2C3=O)C1(*)[Si+]* Chemical compound *C(C(*)(CC1(*)C2C(O3)=O)C2C3=O)C1(*)[Si+]* 0.000 description 2
- 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 2
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OQJPAHYVGNJBJK-UHFFFAOYSA-N (3-dimethylsilylphenyl)-dimethylsilane Chemical compound C[SiH](C)C1=CC=CC([SiH](C)C)=C1 OQJPAHYVGNJBJK-UHFFFAOYSA-N 0.000 description 1
- DRDSKOMREAIEJM-UHFFFAOYSA-N (4-diethylsilylphenyl)-diethylsilane Chemical compound CC[SiH](CC)C1=CC=C([SiH](CC)CC)C=C1 DRDSKOMREAIEJM-UHFFFAOYSA-N 0.000 description 1
- WJPCIELTJWREGF-UHFFFAOYSA-N (4-diphenylsilylphenyl)-diphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC(=CC=1)[SiH](C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 WJPCIELTJWREGF-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- QYXVDGZUXHFXTO-UHFFFAOYSA-L 3-oxobutanoate;platinum(2+) Chemical compound [Pt+2].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O QYXVDGZUXHFXTO-UHFFFAOYSA-L 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
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- KNRCVAANTQNTPT-UHFFFAOYSA-N methyl-5-norbornene-2,3-dicarboxylic anhydride Chemical compound O=C1OC(=O)C2C1C1(C)C=CC2C1 KNRCVAANTQNTPT-UHFFFAOYSA-N 0.000 description 1
- NKNJIRBQVXUCAQ-UHFFFAOYSA-N n,n-dimethylacetamide;oxolane Chemical compound C1CCOC1.CN(C)C(C)=O NKNJIRBQVXUCAQ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Abstract
Description
本発明は、ケイ素含有テトラカルボン酸二無水物に関し、さらに詳述すると、ポリアミド酸およびポリイミドの原料として有用なケイ素含有テトラカルボン酸二無水物、その製造方法ならびにポリイミド樹脂に関する。 The present invention relates to a silicon-containing tetracarboxylic acid dianhydride, and more particularly to a silicon-containing tetracarboxylic acid dianhydride useful as a raw material for a polyamic acid and a polyimide, a method for producing the same, and a polyimide resin.
従来、ポリイミド樹脂は、耐熱性、耐燃性、電気・機械的特性などを有する樹脂として知られており、銅張積層板、多層プリント配線板材料などの複合材料として使用されている。また、ポリイミド樹脂は、ＬＳＩ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、液晶配線向膜などのワニスとして、またフレキシブルプリント配線板基板などのフィルムとしても利用されている。
しかし、一般的なポリイミド樹脂は、芳香族テトラカルボン酸二無水物を原料とするものであり、高耐熱性である一方で、光透過性や有機溶剤への溶解性に乏しいという問題がある。
この点、光学分野での使用を目的に、光透過性を向上させるため、脂環式テトラカルボン酸二無水物を原料としたポリイミドが提案されている（特許文献１，２）が、これらのポリイミドも有機溶剤への溶解性は不十分であるうえ、合成方法が煩雑で高コストとなるという問題がある。
Conventionally, polyimide resin is known as a resin having heat resistance, flame resistance, electrical / mechanical properties, etc., and is used as a composite material such as a copper-clad laminate and a multilayer printed wiring board material. The polyimide resin is used as a passion film for LSI multilayer wiring, an α-ray blocking film for memory elements, a multilayer wiring insulating film such as a magnetic head, a varnish for liquid crystal wiring facing film, and a film for flexible printed wiring board substrates. Is also used.
However, a general polyimide resin is made from an aromatic tetracarboxylic dianhydride and has high heat resistance, but has a problem of poor light transmittance and poor solubility in an organic solvent.
In this regard, polyimides made from an alicyclic tetracarboxylic dianhydride as a raw material have been proposed in order to improve light transmission for use in the optical field (
本発明は、上記事情に鑑みなされたもので、有機溶剤への溶解性および光透過性に優れるポリイミド樹脂を与えるテトラカルボン酸二無水物、その製造方法およびポリイミド樹脂を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a tetracarboxylic dianhydride, a method for producing the same, and a polyimide resin, which provide a polyimide resin having excellent solubility in an organic solvent and light transmittance. ..
本発明者は、上記課題を解決すべく鋭意検討した結果、ケイ素原子を含有する所定のテトラカルボン酸二無水物が、有機溶剤への溶解性および光透過性に優れるポリイミド樹脂を与えることを見出し、本発明を完成した。 As a result of diligent studies to solve the above problems, the present inventor has found that a predetermined tetracarboxylic dianhydride containing a silicon atom provides a polyimide resin having excellent solubility in an organic solvent and light transmittance. , The present invention has been completed.
即ち、本発明は、
１． 下記一般式（１）で表されるケイ素含有テトラカルボン酸二無水物、
（式中、Ｒ1は、それぞれ独立に炭素原子数１〜１２の一価炭化水素基であり、Ｒ2は、それぞれ独立に水素原子または炭素原子数１〜１２の一価炭化水素基であり、Ａは、下記構造式（２）
２． 下記一般式（３）で表されるシラン化合物と、下記一般式（４）で表される酸無水物とをヒドロシリル化反応させる１記載のケイ素含有テトラカルボン酸二無水物の製造方法、
３． １記載のケイ素含有テトラカルボン酸二無水物を含む単量体の重合物であるポリイミド樹脂
を提供する。
That is, the present invention
1. 1. Silicon-containing tetracarboxylic dianhydride represented by the following general formula (1),
(In the formula, R 1 is an independently monovalent hydrocarbon group having 1 to 12 carbon atoms, and R 2 is an independent hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms, respectively. , A is the following structural formula (2)
2. 2. The method for producing a silicon-containing tetracarboxylic acid dianhydride according to 1, wherein the silane compound represented by the following general formula (3) and the acid anhydride represented by the following general formula (4) are hydrosilylated.
3. 3. A polyimide resin which is a polymer of a monomer containing the silicon-containing tetracarboxylic dianhydride according to 1 is provided.
本発明のケイ素含有テトラカルボン酸二無水物は、ポリイミドの原料に使用することができる。本発明のケイ素含有テトラカルボン酸二無水物を原料に使用したポリイミドは、有機溶剤への溶解性および光透過性に優れ、光学用途などに有用である。 The silicon-containing tetracarboxylic dianhydride of the present invention can be used as a raw material for polyimide. The polyimide using the silicon-containing tetracarboxylic dianhydride of the present invention as a raw material has excellent solubility in an organic solvent and light transmission, and is useful for optical applications and the like.
以下、本発明をさらに詳しく説明する。
本発明のケイ素含有テトラカルボン酸二無水物は、下記一般式（１）で表される。
Hereinafter, the present invention will be described in more detail.
The silicon-containing tetracarboxylic dianhydride of the present invention is represented by the following general formula (1).
式（１）中、Ｒ1は、それぞれ独立に炭素原子数１〜１２の一価炭化水素基であり、Ｒ2は、それぞれ独立に水素原子または炭素原子数１〜１２の一価炭化水素基である。
Ｒ1およびＲ2の炭素原子数１〜１２の一価炭化水素基としては、直鎖、分岐、環状のいずれでもよく、具体例としては、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｎ−オクチル、シクロヘキシル基等のアルキル基、フェニル、トリル、ナフチル基等のアリール基などが挙げられる。これらの中でも原料入手の点から、Ｒ1およびＲ2は、炭素原子数１〜６のアルキル基が好ましく、メチル基がより好ましい。
In the formula (1), R 1 is an independently monovalent hydrocarbon group having 1 to 12 carbon atoms, and R 2 is an independent hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms. Is.
The monovalent hydrocarbon group having 1 to 12 carbon atoms of R 1 and R 2 may be linear, branched or cyclic, and specific examples thereof are methyl, ethyl, n-propyl, isopropyl and n-butyl. , Alkyl groups such as isobutyl, n-octyl and cyclohexyl groups, aryl groups such as phenyl, trill and naphthyl groups and the like. Among these, from the viewpoint of obtaining raw materials, R 1 and R 2 are preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group.
Ａは、下記構造式（２）で表される二価の基であり、破線は、結合手を表す。 A is a divalent group represented by the following structural formula (2), and the broken line represents a bond.
本発明のケイ素含有テトラカルボン酸二無水物の具体例としては、下記のものが例示される。 Specific examples of the silicon-containing tetracarboxylic dianhydride of the present invention include the following.
本発明のケイ素含有テトラカルボン酸二無水物は、例えば、下記一般式（３）で表されるシラン化合物と、下記一般式（４）で表される酸無水物とをヒドロシリル化反応させることにより得られる。 The silicon-containing tetracarboxylic acid dianhydride of the present invention is obtained by, for example, hydrosilylating a silane compound represented by the following general formula (3) with an acid anhydride represented by the following general formula (4). can get.
式（３）および（４）中、Ｒ1およびＲ2は、上記式（１）中のＲ1およびＲ2と同じである。 In the formula (3) and (4), R 1 and R 2 are the same as R 1 and R 2 in the formula (1).
シラン化合物（３）の具体例としては、１，４−ビス（ジメチルシリル）ベンゼン、１，４−ビス（ジエチルシリル）ベンゼン、１，４−ビス（ジフェニルシリル）ベンゼン、１，３−ビス（ジメチルシリル）ベンゼンなどが挙げられる。 Specific examples of the silane compound (3) include 1,4-bis (dimethylsilyl) benzene, 1,4-bis (diethylsilyl) benzene, 1,4-bis (diphenylsilyl) benzene, and 1,3-bis ( Dimethylsilyl) benzene and the like can be mentioned.
酸無水物（４）の具体例としては、５−ノルボルネン−２，３−ジカルボン酸無水物、メチル−５−ノルボルネン−２，３−ジカルボン酸無水物、エチル−５−ノルボルネン−２，３−ジカルボン酸無水物などが挙げられる。 Specific examples of the acid anhydride (4) include 5-norbornene-2,3-dicarboxylic acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, and ethyl-5-norbornene-2,3-. Examples thereof include dicarboxylic acid anhydride.
シラン化合物（３）と酸無水物（４）の使用量は、シラン化合物中のＳｉ−Ｈ基１モルに対し、酸無水物中の炭素−炭素二重結合の量が１．０〜３．０モルとなる量が好ましい。 The amount of the silane compound (3) and the acid anhydride (4) used is such that the amount of carbon-carbon double bond in the acid anhydride is 1.0 to 3. An amount of 0 mol is preferable.
ヒドロシリル化反応触媒としては、従来から公知のものを全て使用することができる。例えば、白金金属を担持したカーボン粉末、白金黒、塩化第２白金、塩化白金酸、塩化白金酸と一価アルコールとの反応生成物、白金とジビニルテトラメチルジシロキサン等のビニルシロキサンとの錯体；塩化白金酸とオレフィン類との錯体、白金ビスアセトアセテート等の白金系触媒；パラジウム系触媒；ロジウム系触媒などの白金族金属系触媒が挙げられる。 As the hydrosilylation reaction catalyst, all conventionally known catalysts can be used. For example, carbon powder carrying platinum metal, platinum black, second platinum chloride, platinum chloride acid, reaction product of platinum chloride acid and monovalent alcohol, complex of platinum and vinyl siloxane such as divinyltetramethyldisiloxane; Examples thereof include a complex of platinum chloride acid and olefins, a platinum-based catalyst such as platinum bisacetoacetate; a platinum-based catalyst; and a platinum group metal-based catalyst such as a rhodium-based catalyst.
触媒の使用量は、触媒としての有効量でよく、特に限定されないが、通常、上記シラン化合物と酸無水物の合計質量に対して、白金族金属の質量基準で好ましくは１〜５００ｐｐｍ、特に好ましくは２〜２００ｐｐｍ程度を配合するとよい。 The amount of the catalyst used may be an effective amount as a catalyst and is not particularly limited, but is usually preferably 1 to 500 ppm, particularly preferably 1 to 500 ppm based on the mass of the platinum group metal with respect to the total mass of the silane compound and the acid anhydride. It is advisable to add about 2 to 200 ppm.
上記付加反応（ヒドロシリル化反応）は溶媒を用いなくても進行するが、溶媒を用いることにより穏和な条件で反応を行うことができる。溶媒としては、例えば、トルエン、キシレン等の芳香族炭化水素系溶媒；ヘキサン、オクタン等の脂肪族炭化水素系溶媒；テトラヒドロフラン、ジオキサン等のエーテル系溶媒などが挙げられ、これらは１種単独であるいは２種以上を組み合わせて用いることができる。 The above addition reaction (hydrosilylation reaction) proceeds without using a solvent, but the reaction can be carried out under mild conditions by using a solvent. Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane and octane; ether solvents such as tetrahydrofuran and dioxane, and these may be used alone or. Two or more types can be used in combination.
反応温度は、２０〜１５０℃が好ましく、５０〜１２０℃がより好ましく、反応時間は、１〜２４時間が好ましい。 The reaction temperature is preferably 20 to 150 ° C, more preferably 50 to 120 ° C, and the reaction time is preferably 1 to 24 hours.
このようにして得られる本発明のケイ素含有テトラカルボン酸二無水物は、ポリアミド酸やポリイミドなどの原料として有用である。本発明のケイ素含有テトラカルボン酸二無水物をモノマーとして上記樹脂を製造することで、透明性および有機溶剤への溶解性の高い樹脂を得ることができる。 The silicon-containing tetracarboxylic dianhydride of the present invention thus obtained is useful as a raw material for polyamic acid, polyimide and the like. By producing the above resin using the silicon-containing tetracarboxylic dianhydride of the present invention as a monomer, a resin having high transparency and high solubility in an organic solvent can be obtained.
ポリイミド樹脂を合成する際に用いられるジアミン化合物としては、特に限定されるものではなく、従来公知のジアミン化合物から適宜選択して用いることができ、その具体例としては、テトラメチレンジアミン、１，４−ジアミノシクロヘキサン、４，４’−ジアミノジシクロヘキシルメタン等の脂肪族ジアミン；ｏ−フェニレンジアミン、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、４，４’−ジアミノジフェニルエーテル、２，２−ビス（４−アミノフェニル）プロパン、２，２−ビス［４−（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などが挙げられ、これらはそれぞれ１種単独で用いても、２種以上組み合わせて用いてもよい。
なお、本発明においては、上述したケイ素含有テトラカルボン酸二無水物とともに、ポリイミド製造に用いられる公知のテトラカルボン酸二無水物を併用してもよいが、透明性および有機溶剤への溶解性を高めるという観点からは、本発明のケイ素含有テトラカルボン酸二無水物を単独で用いることが好ましい。
The diamine compound used when synthesizing the polyimide resin is not particularly limited, and can be appropriately selected from conventionally known diamine compounds and used. Specific examples thereof include tetramethylenediamine, 1,4. An aliphatic diamine such as −diaminocyclohexane, 4,4′-diaminodicyclohexylmethane; o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylether, 2,2-bis (4-amino). Examples thereof include aromatic diamines such as phenyl) propane and 2,2-bis [4- (4-aminophenoxy) phenyl] propane, and these may be used alone or in combination of two or more. good.
In the present invention, a known tetracarboxylic dianhydride used for producing polyimide may be used in combination with the above-mentioned silicon-containing tetracarboxylic dianhydride, but the transparency and solubility in an organic solvent may be obtained. From the viewpoint of enhancing, it is preferable to use the silicon-containing tetracarboxylic dianhydride of the present invention alone.
また、本発明のポリイミド樹脂は、公知の方法で製造することができる。
例えば、まず、ケイ素含有テトラカルボン酸二無水物およびジアミン化合物を溶剤中に仕込み、２０〜５０℃程度で反応させて、ポリイミド樹脂の前駆体であるポリアミド酸を製造する。次に、得られたポリアミド酸の溶液を、好ましくは６０〜２００℃に昇温し、ポリアミック酸の酸アミドを脱水閉環反応させてポリイミド樹脂の溶液を得た後、この溶液を、水、メタノール、エタノール、アセトニトリル等の溶剤に投入して沈殿させ、生じた沈殿物を乾燥することにより、ポリイミド樹脂を得ることができる。
Further, the polyimide resin of the present invention can be produced by a known method.
For example, first, a silicon-containing tetracarboxylic dianhydride and a diamine compound are charged in a solvent and reacted at about 20 to 50 ° C. to produce a polyamic acid which is a precursor of a polyimide resin. Next, the obtained polyamic acid solution is heated to preferably 60 to 200 ° C., and the acid amide of the polyamic acid is dehydrated and ring-closed to obtain a polyimide resin solution. , Ethanol, acetonitrile and the like to precipitate, and the resulting precipitate is dried to obtain a polyimide resin.
本発明のポリイミド樹脂の重量平均分子量は、特に限定されるものではないが、当該樹脂から得られる皮膜の強度と、溶剤への溶解性とのバランスを考慮すると、５，０００〜１００，０００が好ましく、１０，０００〜５０，０００がより好ましい。
なお、本発明における重量平均分子量は、テトラヒドロフラン（ＴＨＦ）を溶媒とするゲル浸透クロマトグラフィー（以下、ＧＰＣと略すこともある）によるポリスチレン換算値である。
The weight average molecular weight of the polyimide resin of the present invention is not particularly limited, but is 5,000 to 100,000 in consideration of the balance between the strength of the film obtained from the resin and the solubility in a solvent. It is preferable, 10,000 to 50,000 is more preferable.
The weight average molecular weight in the present invention is a polystyrene-equivalent value obtained by gel permeation chromatography (hereinafter, may be abbreviated as GPC) using tetrahydrofuran (THF) as a solvent.
以下、実施例および比較例を用いて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
［実施例１−１］ケイ素含有テトラカルボン酸二無水物の製造
撹拌装置、冷却管、滴下ロートおよび温度計を備えた５００ｍＬの４つ口フラスコに、５−ノルボルネン−２，３−ジカルボン酸無水物２５．０ｇ（１５２ミリモル）およびトルエン６２．５ｇを加え、撹拌しながらオイルバスを用いて８０℃に加熱した。これに、２質量％塩化白金酸のエタノール溶液０．２２ｇを添加し、撹拌しながら１，４−ビス（ジメチルシリル）ベンゼン８．８８ｇ（４５．７ミリモル）を１５分かけて滴下した。滴下終了後、さらに９０℃で２時間加熱撹拌し、その後室温まで冷却した。析出した白色沈殿を濾別し、濾物にトルエン４０ｇを加え、１３０℃で３０分撹拌した。室温まで冷却した後、析出した白色沈殿を濾別した。得られた濾物を５０℃、０．４ｋＰａの環境で乾燥し、白色固体１５．３ｇ（収率６４％）を得た。
この白色固体をＩＲおよび1Ｈ−ＮＭＲで分析した結果、下記構造式（５）で表されるケイ素含有テトラカルボン酸二無水物であることが確認された。ＩＲおよび1Ｈ−ＮＭＲ測定結果を図１および図２に示す。
[Example 1-1] Production of silicon-containing tetracarboxylic acid anhydride In a 500 mL four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a thermometer, 5-norbornen-2,3-dicarboxylic acid anhydride was added. 25.0 g (152 mmol) of the product and 62.5 g of toluene were added, and the mixture was heated to 80 ° C. using an oil bath with stirring. To this, 0.22 g of an ethanol solution of 2 mass% chloroplatinic acid was added, and 8.88 g (45.7 mmol) of 1,4-bis (dimethylsilyl) benzene was added dropwise over 15 minutes with stirring. After completion of the dropping, the mixture was further heated and stirred at 90 ° C. for 2 hours, and then cooled to room temperature. The precipitated white precipitate was separated by filtration, 40 g of toluene was added to the filtrate, and the mixture was stirred at 130 ° C. for 30 minutes. After cooling to room temperature, the precipitated white precipitate was filtered off. The obtained filter medium was dried in an environment of 50 ° C. and 0.4 kPa to obtain 15.3 g (yield 64%) of a white solid.
As a result of analyzing this white solid by IR and 1 H-NMR, it was confirmed that it was a silicon-containing tetracarboxylic dianhydride represented by the following structural formula (5). The IR and 1 1 H-NMR measurement results are shown in FIGS. 1 and 2.
1Ｈ−ＮＭＲ：７．４６ｐｐｍ（４Ｈ，ｓ，Ｈi）、２．９６〜２．８９ｐｐｍ（４Ｈ，ｍ，Ｈb,c）、２．８３〜２．７７ｐｐｍ（４Ｈ，ｍ，Ｈa,d）、１．６９〜１．５４ｐｐｍ（４Ｈ，ｍ，Ｈf,g）、１．１８〜１．１１ｐｐｍ（４Ｈ，ｍ，Ｈf,g）、０．９４〜０．８６ｐｐｍ（２Ｈ，ｍ，Ｈe）、０．３１ｐｐｍ、および０．３０ｐｐｍ（１２Ｈ，ｓ，Ｈh） 1 H-NMR: 7.46ppm (4H , s, H i), 2.96~2.89ppm (4H, m, H b, c), 2.83~2.77ppm (4H, m, H a, d ), 1.69 to 1.54 ppm (4H, m, H f, g ), 1.18 to 1.11 ppm (4H, m, H f, g ), 0.94 to 0.86 ppm (2H, m). , H e), 0.31ppm, and 0.30ppm (12H, s, H h )
［実施例２−１］ポリイミド樹脂の製造
撹拌装置、冷却管および温度計を備えた１００ｍＬの３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１．５７ｇ（３．８２ミリモル）およびＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）１４．３ｇを加え、撹拌して均一になったところに、実施例１−１で得られた化合物２．００ｇ（３．８３ミリモル）を加え、室温で１７時間撹拌を続けた。次に、トリエチルアミン１．１６ｇ（１１．５ミリモル）、無水酢酸１．１７ｇ（１１．５ミリモル）を順に加え、８０℃で３時間イミド化を行った。溶液を室温まで冷却した後、５０ｇのメタノールに滴下して沈殿を析出させた。沈殿を濾別し、５０ｇのメタノールで洗浄後、８０℃、０．４ｋＰａの環境で乾燥し、白色粉末状の樹脂２．９６ｇ（収率８７％）を得た。ＴＨＦを溶媒とするＧＰＣにより、この樹脂の重量平均分子量（ポリスチレン換算）を測定したところ、２１，０００であった。
得られた樹脂のＩＲスペクトルを図３に示す。１７０６および１７７４ｃｍ-1にイミドカルボニル由来のＣ＝Ｏ伸縮振動が見られることから、ポリイミド樹脂であることが確認された。
[Example 2-1] Production of polyimide resin 1.57 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane in a 100 mL three-necked flask equipped with a stirrer, a cooling tube and a thermometer. (3.82 mmol) and 14.3 g of N, N-dimethylacetamide (DMAc) were added, and the mixture was stirred to make it uniform. Then, 2.00 g (3.83 mmol) of the compound obtained in Example 1-1 was added. ) Was added, and stirring was continued at room temperature for 17 hours. Next, 1.16 g (11.5 mmol) of triethylamine and 1.17 g (11.5 mmol) of acetic anhydride were added in this order, and imidization was performed at 80 ° C. for 3 hours. After cooling the solution to room temperature, the solution was added dropwise to 50 g of methanol to precipitate a precipitate. The precipitate was separated by filtration, washed with 50 g of methanol, and dried in an environment of 80 ° C. and 0.4 kPa to obtain 2.96 g (yield 87%) of a white powdery resin. The weight average molecular weight (in terms of polystyrene) of this resin was measured by GPC using THF as a solvent and found to be 21,000.
The IR spectrum of the obtained resin is shown in FIG. Since C = O expansion and contraction vibrations derived from imidecarbonyl were observed at 1706 and 1774 cm- 1 , it was confirmed that the resin was a polyimide resin.
得られた樹脂は、クロロホルム、ＴＨＦ、およびＤＭＡｃに溶解した。 The obtained resin was dissolved in chloroform, THF, and DMAc.
得られた樹脂を１０質量％のＴＨＦ溶液とし、枠を設けたスライドガラス上に広げ、４０℃１時間、次いで８０℃１時間の環境下にさらし、１５μｍ厚みのフィルムを作製した。分光光度計（Ｕ３３１０型（（株）日立製作所製））を用いてこのフィルムが付いたガラスの光透過率、およびガラス単体の光透過率を測定し、その差からフィルムの透過率を算出したところ、波長４００〜８００ｎｍの範囲で９８％以上であった。 The obtained resin was made into a 10 mass% THF solution, spread on a slide glass provided with a frame, and exposed to an environment of 40 ° C. for 1 hour and then at 80 ° C. for 1 hour to prepare a film having a thickness of 15 μm. Using a spectrophotometer (U3310 type (manufactured by Hitachi, Ltd.)), the light transmittance of the glass with this film and the light transmittance of the glass alone were measured, and the transmittance of the film was calculated from the difference. However, it was 98% or more in the wavelength range of 400 to 800 nm.
上記のように、本発明のケイ素含有テトラカルボン酸二無水物を原料に使用したポリイミド樹脂は、有機溶剤への溶解性、および光透過性に優れる材料となることが示された。 As described above, it has been shown that the polyimide resin using the silicon-containing tetracarboxylic dianhydride of the present invention as a raw material is a material having excellent solubility in an organic solvent and light transmission.
Claims (3)
（式中、Ｒ1は、それぞれ独立に炭素原子数１〜１２の一価炭化水素基であり、Ｒ2は、それぞれ独立に水素原子または炭素原子数１〜１２の一価炭化水素基であり、Ａは、下記構造式（２）
(In the formula, R 1 is an independently monovalent hydrocarbon group having 1 to 12 carbon atoms, and R 2 is an independent hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms, respectively. , A is the following structural formula (2)
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