JPH048734A - Fluorinated polyimide copolymer and its preparation - Google Patents
Fluorinated polyimide copolymer and its preparationInfo
- Publication number
- JPH048734A JPH048734A JP11049890A JP11049890A JPH048734A JP H048734 A JPH048734 A JP H048734A JP 11049890 A JP11049890 A JP 11049890A JP 11049890 A JP11049890 A JP 11049890A JP H048734 A JPH048734 A JP H048734A
- Authority
- JP
- Japan
- Prior art keywords
- formulas
- formula
- group
- fluorinated polyimide
- diaminobiphenyl
- 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
- 229920001721 polyimide Polymers 0.000 title claims description 33
- 239000004642 Polyimide Substances 0.000 title claims description 32
- 239000000126 substance Substances 0.000 claims abstract description 9
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000000962 organic group Chemical group 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 5
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 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 5
- 150000004985 diamines Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000009102 absorption Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Optical Integrated Circuits (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は屈折率を自由に制御できるフッ素化ポリイミド
共重合体及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a fluorinated polyimide copolymer whose refractive index can be freely controlled and a method for producing the same.
ポリイミドは種々の有機ポリマーの中で耐熱性に優れて
いるため、宇宙、航空分野から電子通信分野まで幅広く
使われ始めている。特に最近では、単に耐熱性に優れて
いるだけでなく、用途に応じて種々の性能を合せ持つこ
とが期待されている。例えばプリント板や、ＬＳＩ用の
層間絶縁膜などでは、熱膨張係数、誘電率が小さいこと
が期待され、光通信関係特に光導波路のクラツド材には
屈折率が小さいことが期待されている。また、安定な物
性値を保つには、吸水率の小さなことが必要である。し
かしながら、これらの性能に充分満足のいくポリイミド
は得られていない。これらのポリイミドを得るた袷には
、ポリイミドの主鎖をできる限り剛直構造にして低熱膨
張性を発現させ、更にモノマーであるテトラカルボン酸
二無水物又はジアミンに低誘電率性、低屈折率性を発現
する置換基を導入する方法が考えられる。例えばエポキ
シ樹脂においては、ジャーナル オブ ポリマー サイ
エンス（Ｊｏｕｒｎａｌ ｏｆ Ｐｏｌｙｍｅｒ ５ｃ
ｉｅｎｃｅ）のノマート（Ｐａｒｔ） Ｃ、ポリマー
レターズ（Ｐｏｌｙｍｅｒ Ｌｅｔｔｅｒｓ）、第２４
巻、第２４９頁（１９８６）に示されているようにエポ
キシ樹脂の硬化剤に多フツ素置換基を導入することによ
り、これまでのエポキシ樹脂の中で最も低い誘電率を達
成している。また特開昭６１−４４９６９号公報で示さ
れているように、屈折率においても多フツ素置換基を導
入することにより、これまでのエポキシ樹脂の中で最も
低い屈折率を達成している。このようにポリイミド骨格
を剛直構造にし、フッ素置換基を導入することにより、
熱膨張係数、誘電率、屈折率の低減が期待できる。Among various organic polymers, polyimide has excellent heat resistance, so it is beginning to be used in a wide range of fields, from space and aviation to electronic communications. Particularly recently, materials are expected not only to have excellent heat resistance but also to have various performances depending on the purpose. For example, printed circuit boards and interlayer insulating films for LSIs are expected to have low coefficients of thermal expansion and dielectric constants, and cladding materials for optical communications, particularly optical waveguides, are expected to have low refractive indexes. In addition, in order to maintain stable physical property values, it is necessary to have a low water absorption rate. However, a polyimide that fully satisfies these properties has not been obtained. To obtain these polyimides, the main chain of the polyimide is made as rigid as possible to exhibit low thermal expansion, and the monomer tetracarboxylic dianhydride or diamine has low dielectric constant and low refractive index properties. One possible method is to introduce a substituent that expresses For example, regarding epoxy resins, the Journal of Polymer Science (Journal of Polymer 5c)
ience) nomato (Part) C, polymer
Letters (Polymer Letters), No. 24
As shown in Vol., p. 249 (1986), the lowest dielectric constant of any epoxy resin to date has been achieved by introducing a polyfluorine substituent into the curing agent of the epoxy resin. Furthermore, as shown in JP-A No. 61-44969, the lowest refractive index of any epoxy resin to date has been achieved by introducing a polyfluorine substituent. By making the polyimide skeleton into a rigid structure and introducing fluorine substituents in this way,
Reductions in thermal expansion coefficient, dielectric constant, and refractive index can be expected.
しかしながら、これまでに剛直構造のポリイミドにフッ
素置換基を導入して、低誘電率、低屈折率、低熱膨張係
数を達成したという報告１まない。However, to date, there have been no reports of achieving low dielectric constant, low refractive index, and low coefficient of thermal expansion by introducing fluorine substituents into polyimide having a rigid structure.
本発明者らは、特願平１−２０１１７０号Ｉこお（１）
でジアミン成分として２．２′−ビス（トリフルオロメ
チル）−４，４’−ジアミノビフェニルを用いたフッ素
化ポリイミドが誘電率、屈折率ともポリイミドとして非
常に小さい値を持つことを示した。The inventors of the present invention have proposed patent application No. 1-201170 (1).
It was shown that a fluorinated polyimide using 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl as the diamine component has very small dielectric constant and refractive index values for a polyimide.
このポリイミドの運用先の一つとして光導波路が考えら
れるが光導波路に使用する場合は、芯材とさや材の屈折
率を自由に制御する必要がある。特願平１−２０１１７
０号明細書で示したフッ素化ポリイミドの屈折率は１．
４９〜１．７１（Ｄ間に入るが、その間を細かく制御す
ることができなし）。Optical waveguides are one possible application for this polyimide, but when used in optical waveguides, it is necessary to freely control the refractive index of the core material and sheath material. Patent application Hei 1-20117
The refractive index of the fluorinated polyimide shown in the specification of No. 0 is 1.
49 to 1.71 (falls between D, but cannot control finely between them).
本発明の目的は屈折率を自由に制御できるポリイミド材
料を提供することにある。An object of the present invention is to provide a polyimide material whose refractive index can be freely controlled.
本発明を概説すれば、本発明の第１の発明は含フツ素化
ポリイミド共重合体に関する発明であって、下記一般式
■：
で表される繰返し単位と下記一般式■：で表される基よ
りなる群からＲ１とＲりが同じにならないように選択し
た４価の有機基を示す）で表される繰返し単位を同一化
学構造中に持つことを特徴とする。To summarize the present invention, the first invention of the present invention relates to a fluorinated polyimide copolymer, which has a repeating unit represented by the following general formula (■) and a repeating unit represented by the following general formula (■): It is characterized by having a repeating unit represented by (representing a tetravalent organic group selected from the group consisting of groups such that R1 and R2 are not the same) in the same chemical structure.
また、本発明の第２の発明は第１の発明の含フツ素化ポ
リイミド共重合体の製造方法に関する発明であって、下
記構造式■：
（式中Ｒ，はＲ３下記の構造式：
で表される２、２′−ビス（トリフルオロメチル）４．
４′−ジアミノビフェニルと、下記構造式■・・・ ［
ｒＶＩ
で表されるテトラカルボン酸二無水物よりなる群から２
種類のテトラカルボン酸二無水物とを反応させることを
特徴とする。Further, the second invention of the present invention is an invention relating to a method for producing the fluorinated polyimide copolymer of the first invention, which has the following structural formula 2,2'-bis(trifluoromethyl) represented4.
4'-diaminobiphenyl and the following structural formula ■... [
2 from the group consisting of tetracarboxylic dianhydrides represented by rVI
It is characterized by reacting with different kinds of tetracarboxylic dianhydrides.
本発明者らは、これまでに得てきた低屈折率フッ素化ポ
リイミドと比較的屈折率の大きいフッ素化ポリイミドの
分子設計技術、合成技術を駆使した屈折率制御法につい
て種々検討した結果、上記式■のジアミンと２種類の酸
二無水物を用いてフッ素化ポリイミド共重合体を得るこ
とにより、屈折率を自由に制御できることを見出した。As a result of various studies on refractive index control methods that make full use of molecular design technology and synthesis technology for fluorinated polyimides with low refractive index and fluorinated polyimide with relatively high refractive index, the present inventors found that the above formula It has been found that the refractive index can be freely controlled by obtaining a fluorinated polyimide copolymer using diamine (2) and two types of acid dianhydrides.
本発明の構成要素の２．２′−ビス（トリフルオロメチ
ル）−４，４’−ジアミノビフェニルの製造方法は、例
えば日本化学会誌、第１９７２巻第３号、６７５〜６７
６頁（１９７２）に記載されている。また、本発明に用
いるテトラカルボン酸二無水物の中でピロメリット酸の
ベンゼン環にフルオロアルキル基を導入した含フツ素酸
二無水物であるトリフルオロメチルピロメリット酸二無
水物、１，４−ジ（トリフルオロメチル）ピロメリット
酸二無水物の製造方法は特願昭６３−１６５０５６号明
細書に記載されている。これらのジアミンと２種類のテ
トラカルボン酸二無水物を反応させることによりポリア
ミック酸の共重合体を製造する。The method for producing 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, which is a component of the present invention, is described, for example, in Journal of the Chemical Society of Japan, Vol. 1972, No. 3, 675-67.
6 (1972). Among the tetracarboxylic dianhydrides used in the present invention, trifluoromethylpyromellitic dianhydride, 1,4, which is a fluorine-containing dianhydride in which a fluoroalkyl group is introduced into the benzene ring of pyromellitic acid, The method for producing -di(trifluoromethyl)pyromellitic dianhydride is described in Japanese Patent Application No. 165056/1983. A polyamic acid copolymer is produced by reacting these diamines with two types of tetracarboxylic dianhydrides.
反応条件は通常のポリアミック酸の重合条件と同じでよ
く、−船釣にはＮ−メチル−２−ピロリドン、Ｎ、Ｎ−
ジメチルアセトアミド、ジメチルホルムアミドなどの極
性有機溶媒中で反応させる。The reaction conditions may be the same as those for ordinary polyamic acid polymerization;
The reaction is carried out in a polar organic solvent such as dimethylacetamide or dimethylformamide.
次に得られたポリアミック酸のイミド化によるポリイミ
ドの合成であるが、これも通常のポリイミドの合成法が
使用できる。Next, polyimide is synthesized by imidizing the obtained polyamic acid, and a conventional polyimide synthesis method can also be used for this.
以下実施例により本発明のフッ素化ポリイミド共重合体
及びその製造方法について詳細に説明するが、本発明は
これら実施例に限定されない。イミド化の確認は赤外吸
収スペクトルにおけるカルボニル基の対称及び非対称伸
縮振動による特性吸収から行った。また、下記各側中、
屈折率はナトリウムＤ線の波長（５８９，６ｎ［１１）
での値である。熱分解温度は窒素気流下１０℃／分の昇
温速度で測定した。The fluorinated polyimide copolymer of the present invention and the method for producing the same will be explained in detail below with reference to Examples, but the present invention is not limited to these Examples. Imidization was confirmed by the characteristic absorption caused by symmetric and asymmetric stretching vibrations of the carbonyl group in the infrared absorption spectrum. In addition, in each side below,
The refractive index is the wavelength of the sodium D line (589,6n [11)
This is the value at Thermal decomposition temperature was measured at a heating rate of 10° C./min under a nitrogen stream.
参考例１
三角フラスコにピロメリット酸二無水物４．３６ｇ （
２０，０ｍｍｏｌ）と弐■の構造式で表される２゜２′
−ビス（トリフルオロメチル）−４，４’−ジアミノビ
フェニル６．４０ ｇ （２０，Ｏｍｍｏｌ） 、及び
Ｎ、Ｎ−ジメチルアセトアミド（ＤＭＡ） １００ｇを
加えた。この混合物を窒素雰囲気下、室温で３日間かく
はんし、ポリアミック酸のＤＭＡ溶液を得た。この溶液
の粘度は約８０ポアズであった。このものをシリコン基
板にスピンコーティングし、窒素雰囲気下で７０℃で２
時間、１６０℃で１時間、２５０℃で３０分、更に３５
０℃で１時間で加熱キュアした。このシリコン基板をは
く離してポリイミドフィルムが得られた。赤外吸収スペ
クトルを測定するとイミド基に特有の吸収が１７４０及
び１７９０ｃｍ−’に現れ、イミド化が完全に進行した
ことが確認できた。このものの熱分解温度は６１０℃、
屈折率は１．６４７であった。Reference Example 1 4.36g of pyromellitic dianhydride in an Erlenmeyer flask (
20,0 mmol) and 2゜2' represented by the structural formula 2
-Bis(trifluoromethyl)-4,4'-diaminobiphenyl 6.40 g (20,0 mmol) and N,N-dimethylacetamide (DMA) 100 g were added. This mixture was stirred at room temperature under a nitrogen atmosphere for 3 days to obtain a DMA solution of polyamic acid. The viscosity of this solution was approximately 80 poise. This material was spin-coated onto a silicon substrate and heated at 70°C under a nitrogen atmosphere for 2 hours.
Time: 1 hour at 160℃, 30 minutes at 250℃, then 35 minutes
It was heated and cured at 0°C for 1 hour. This silicon substrate was peeled off to obtain a polyimide film. When the infrared absorption spectrum was measured, absorptions specific to imide groups appeared at 1740 and 1790 cm-', confirming that imidization had progressed completely. The thermal decomposition temperature of this material is 610℃,
The refractive index was 1.647.
参考例２
参考例１におけるピロメリット酸二無水物を２．２−ビ
ス（３，４−ジカルボキシフェニル）ヘキサフルオロプ
ロパンニ無水物８．８８ ｇ （２０，Ｏｍｍｏｌ）に
置き換えて、参考例１と同様に行った。Reference Example 2 By replacing pyromellitic dianhydride in Reference Example 1 with 8.88 g (20, Ommol) of 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropanide anhydride, Reference Example 1 was prepared. I did the same thing.
合成したポリイミドの特性を後記表１に他の例と共に示
す。The properties of the synthesized polyimide are shown in Table 1 below together with other examples.
参考例３
参考例１におけるピロメリット酸二無水物を３．３’：
４．４’−ベンゾフェノンテトラカルボン酸二無水物６
．４４ ｇ （２０，０ｎｏ＋＋ｏｌ）に置き換えて、
参考例１と同様に行った。合成したポリイミドの特性を
表１に示す。Reference Example 3 Pyromellitic dianhydride in Reference Example 1 was 3.3':
4.4'-benzophenonetetracarboxylic dianhydride 6
．． 44 g (20,0no++ol),
The same procedure as in Reference Example 1 was carried out. Table 1 shows the properties of the synthesized polyimide.
参考例４
参考例１におけるピロメリット酸二無水物を３．１４．
４’−ビフェニルテトラカルボン酸二無水物５．８８
ｇ （２０，０ｍｍｏｌ）に置き換えて、参考例１と同
様に行った。合成したポリイミドの特性を表１に示す。Reference Example 4 The pyromellitic dianhydride in Reference Example 1 was converted to 3.14.
4'-biphenyltetracarboxylic dianhydride 5.88
The same procedure as in Reference Example 1 was carried out except that g (20.0 mmol) was substituted. Table 1 shows the properties of the synthesized polyimide.
参考例５
参考例１にふけるピロメリット酸二無水物をトリフルオ
ロメチルピロメリット酸二無水物５、７２ ｇ （２０
，０ｍｍｏｌ）に置き換えて、参考例１と同様に行った
。合成したポリイミドの特性を表１に示す。Reference Example 5 The pyromellitic dianhydride used in Reference Example 1 was mixed with trifluoromethylpyromellitic dianhydride 5.72 g (20
, 0 mmol) and carried out in the same manner as in Reference Example 1. Table 1 shows the properties of the synthesized polyimide.
参考例６
参考例１におけるピロメリット酸二無水物を１．４−ジ
（トリフルオロメチル）ピロメリット酸二無水物７．０
８ ｇ （２０，０ｍｍｏｌ）に置き換えて、参考例１
と同様に行った。合成したポリイミドの特性を表１に示
す。Reference Example 6 Pyromellitic dianhydride in Reference Example 1 was replaced with 1.4-di(trifluoromethyl)pyromellitic dianhydride 7.0
Reference example 1 by replacing with 8 g (20.0 mmol)
I did the same thing. Table 1 shows the properties of the synthesized polyimide.
実施例１〜２３
参考例１におけるピロメリット酸二無水物を表１に示す
酸無水物の混合物２０． Ｏｍｍｏｌに置き換えて、参
考例１と同様に行った。合成したポリイミド共重合体の
特性を表１に示す。Examples 1 to 23 The pyromellitic dianhydride in Reference Example 1 was converted into a mixture of acid anhydrides shown in Table 1 20. The same procedure as in Reference Example 1 was carried out except that Ommol was used. Table 1 shows the properties of the synthesized polyimide copolymer.
これらの結果から、本発明のフッ素化ポリイミド共重合
体の屈折率は１．４９４から１．６７２まで自由に制御
できることが明らかとなった。These results revealed that the refractive index of the fluorinated polyimide copolymer of the present invention can be freely controlled from 1.494 to 1.672.
以上説明したように、本発明のフッ素化ポリイミド共重
合体は、屈折率を自由に制御できる利点があるため、種
々の形状、寸法、モードの光ファイバ又は光導波路用の
コア材、クラツド材として使用することができる。As explained above, the fluorinated polyimide copolymer of the present invention has the advantage of being able to freely control the refractive index, so it can be used as a core material or cladding material for optical fibers or optical waveguides of various shapes, dimensions, and modes. can be used.
特許出願人 日本電信電話株式会社Patent applicant: Nippon Telegraph and Telephone Corporation
Claims (1)
らないように選択した４価の有機基を示す）で表される
繰返し単位を同一化学構造中に持つことを特徴とするフ
ッ素化ポリイミド共重合体。 ２、下記構造式III： ▲数式、化学式、表等があります▼・・・〔III〕 で表される２，２′−ビス（トリフルオロメチル）−４
，４′−ジアミノビフェニルと、下記構造式IV： ▲数式、化学式、表等があります▼・・・〔IV〕 で表されるテトラカルボン酸二無水物よりな群から２種
類のテトラカルボン酸二無水物とを反応させることを特
徴とする請求項１記載のフッ素化ポリイミド共重合体の
製造方法。[Claims] 1. The following general formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼...The repeating unit represented by [I] and the following general formula II: ▲There are mathematical formulas, chemical formulas, tables, etc. ▼...[II] (In the formula, R_1 and R_2 are the following structural formulas: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 4 selected from the group consisting of the groups represented by A fluorinated polyimide copolymer characterized by having repeating units represented by (representing a valent organic group) in the same chemical structure. 2. Structural formula III below: ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [III] 2,2'-bis(trifluoromethyl)-4
, 4'-diaminobiphenyl, and two types of tetracarboxylic dianhydrides from the group of tetracarboxylic dianhydrides represented by the following structural formula IV: ▲Mathematical formulas, chemical formulas, tables, etc.▼... [IV] 2. The method for producing a fluorinated polyimide copolymer according to claim 1, which comprises reacting the fluorinated polyimide copolymer with an anhydride.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11049890A JP2640553B2 (en) | 1990-04-27 | 1990-04-27 | Fluorinated polyimide copolymer and method for producing the same |
| CA002041133A CA2041133C (en) | 1990-04-27 | 1991-04-24 | Polymide optical waveguide |
| EP91401120A EP0454590B1 (en) | 1990-04-27 | 1991-04-26 | Polyimide optical waveguide |
| US07/692,249 US5108201A (en) | 1990-04-27 | 1991-04-26 | Polyimide optical waveguide |
| DE69120464T DE69120464T2 (en) | 1990-04-27 | 1991-04-26 | Opal polyimide waveguide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11049890A JP2640553B2 (en) | 1990-04-27 | 1990-04-27 | Fluorinated polyimide copolymer and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH048734A true JPH048734A (en) | 1992-01-13 |
| JP2640553B2 JP2640553B2 (en) | 1997-08-13 |
Family
ID=14537287
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11049890A Expired - Lifetime JP2640553B2 (en) | 1990-04-27 | 1990-04-27 | Fluorinated polyimide copolymer and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2640553B2 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0641305A (en) * | 1991-10-25 | 1994-02-15 | Internatl Business Mach Corp <Ibm> | Polyamic acid and polyimide from fluorinated reactant |
| EP0720030A1 (en) | 1994-12-28 | 1996-07-03 | Hoechst Aktiengesellschaft | Waveguide device and method for production thereof |
| US5572619A (en) * | 1993-03-18 | 1996-11-05 | Nippon Telegraph And Telephone Corporation | Polimide optical waveguide |
| JP2002082240A (en) * | 2000-06-22 | 2002-03-22 | Fujikura Ltd | Optical multiplexer/demultiplexer |
| US6750320B2 (en) | 2001-02-20 | 2004-06-15 | Central Glass Company, Limited | Process for producing polyimide platy object |
| US6842576B2 (en) | 2003-05-19 | 2005-01-11 | Nitto Denko Corporation | Polymer lightguide |
| EP1760114A2 (en) | 2005-08-22 | 2007-03-07 | Nippon Shokubai Co., Ltd. | Halogenated polyamide acid composition and its applications |
| JP4786859B2 (en) * | 2000-08-09 | 2011-10-05 | 三井化学株式会社 | Optical member made of polyimide resin |
| WO2013191180A1 (en) * | 2012-06-19 | 2013-12-27 | 新日鉄住金化学株式会社 | Display device, method for manufacturing same, polyimide film for display device supporting bases, and method for producing polyimide film for display device supporting bases |
| KR20160132092A (en) | 2014-07-17 | 2016-11-16 | 아사히 가세이 가부시키가이샤 | Resin precursor, resin composition containing same, polyimide resin membrane, resin film, and method for producing same |
| JP2018109783A (en) * | 2012-06-19 | 2018-07-12 | 新日鉄住金化学株式会社 | Method for manufacturing display |
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1990
- 1990-04-27 JP JP11049890A patent/JP2640553B2/en not_active Expired - Lifetime
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5780199A (en) * | 1991-10-25 | 1998-07-14 | International Business Machines Corporation | Polyamic acid and polyimide from fluorinated reactant |
| JPH0641305A (en) * | 1991-10-25 | 1994-02-15 | Internatl Business Mach Corp <Ibm> | Polyamic acid and polyimide from fluorinated reactant |
| US5572619A (en) * | 1993-03-18 | 1996-11-05 | Nippon Telegraph And Telephone Corporation | Polimide optical waveguide |
| US5598501A (en) * | 1993-03-18 | 1997-01-28 | Nippon Telegraph And Telephone Corporation | Polyimide optical waveguide and method of manufacturing the same |
| EP0720030A1 (en) | 1994-12-28 | 1996-07-03 | Hoechst Aktiengesellschaft | Waveguide device and method for production thereof |
| US5694513A (en) * | 1994-12-28 | 1997-12-02 | Hoechst Aktiengesellschaft | Waveguide device and method for production thereof |
| JP2002082240A (en) * | 2000-06-22 | 2002-03-22 | Fujikura Ltd | Optical multiplexer/demultiplexer |
| JP4786859B2 (en) * | 2000-08-09 | 2011-10-05 | 三井化学株式会社 | Optical member made of polyimide resin |
| US6750320B2 (en) | 2001-02-20 | 2004-06-15 | Central Glass Company, Limited | Process for producing polyimide platy object |
| US6842576B2 (en) | 2003-05-19 | 2005-01-11 | Nitto Denko Corporation | Polymer lightguide |
| US7409139B2 (en) | 2005-08-22 | 2008-08-05 | Nippon Shokubai Co., Ltd. | Halogenated polyamide acid composition and its applications |
| EP1760114A2 (en) | 2005-08-22 | 2007-03-07 | Nippon Shokubai Co., Ltd. | Halogenated polyamide acid composition and its applications |
| WO2013191180A1 (en) * | 2012-06-19 | 2013-12-27 | 新日鉄住金化学株式会社 | Display device, method for manufacturing same, polyimide film for display device supporting bases, and method for producing polyimide film for display device supporting bases |
| CN104380366A (en) * | 2012-06-19 | 2015-02-25 | 新日铁住金化学株式会社 | Display device, method for manufacturing same, polyimide film for display device supporting bases, and method for producing polyimide film for display device supporting bases |
| JP2018109783A (en) * | 2012-06-19 | 2018-07-12 | 新日鉄住金化学株式会社 | Method for manufacturing display |
| KR20160132092A (en) | 2014-07-17 | 2016-11-16 | 아사히 가세이 가부시키가이샤 | Resin precursor, resin composition containing same, polyimide resin membrane, resin film, and method for producing same |
| KR20180100732A (en) | 2014-07-17 | 2018-09-11 | 아사히 가세이 가부시키가이샤 | Resin precursor, resin composition containing same, polyimide resin membrane, resin film, and method for producing same |
| KR20190071842A (en) | 2014-07-17 | 2019-06-24 | 아사히 가세이 가부시키가이샤 | Resin precursor, resin composition containing same, polyimide resin membrane, resin film, and method for producing same |
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|---|---|
| JP2640553B2 (en) | 1997-08-13 |
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