JP3771302B2 - Tetrafluoro- [2,2] -paracyclophane and process for producing the same - Google Patents
Tetrafluoro- [2,2] -paracyclophane and process for producing the same Download PDFInfo
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- JP3771302B2 JP3771302B2 JP20896295A JP20896295A JP3771302B2 JP 3771302 B2 JP3771302 B2 JP 3771302B2 JP 20896295 A JP20896295 A JP 20896295A JP 20896295 A JP20896295 A JP 20896295A JP 3771302 B2 JP3771302 B2 JP 3771302B2
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- Prior art keywords
- paracyclophane
- tetrafluoro
- film
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Links
- 238000000034 method Methods 0.000 title claims description 4
- 239000000126 substance Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims 2
- 239000010408 film Substances 0.000 description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229920000052 poly(p-xylylene) Polymers 0.000 description 9
- 238000005229 chemical vapour deposition Methods 0.000 description 8
- CSJLBAMHHLJAAS-UHFFFAOYSA-N diethylaminosulfur trifluoride Chemical compound CCN(CC)S(F)(F)F CSJLBAMHHLJAAS-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- OOLUVSIJOMLOCB-UHFFFAOYSA-N 1633-22-3 Chemical compound C1CC(C=C2)=CC=C2CCC2=CC=C1C=C2 OOLUVSIJOMLOCB-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- -1 polyparaxylylene Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 0 CC1C=CC(**)CC1 Chemical compound CC1C=CC(**)CC1 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 2
- 229940071536 silver acetate Drugs 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RZXMPPFPUUCRFN-UHFFFAOYSA-N Cc(cc1)ccc1N Chemical compound Cc(cc1)ccc1N RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- QHMQWEPBXSHHLH-UHFFFAOYSA-N sulfur tetrafluoride Chemical compound FS(F)(F)F QHMQWEPBXSHHLH-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は、化学蒸着法によりコーテイング膜を形成するための材料として有用な新規な化合物、テトラフルオロ−［２，２］−パラシクロファンおよびその製造方法に関する。
【０００２】
【従来の技術】
下記構造式（ＩＩＩ）
【化３】
【０００３】
【化４】
このコーテイング法ではあらゆる形状の物体に、その形状通りのコーテイング膜形成が可能であり、このように形成されたポリマー薄膜はガス・バリヤー性、誘電特性に優れ電子部品材料、あるいは宇宙機器部品のコーテイングに広く用いられている。
【０００５】
しかし、上記構造式（ＩＩＩ）からのポリパラキシリレン膜は、その優れた性能にかかわらず、使用に際し、一つの限界を有する。それはポリマー構造において、ベンゼン核を結びつけている−ＣＨ２−ＣＨ２−構造が酸化され易いため、真空中や窒素中では広い使用範囲を有するものの、空気中では使用温度が制限されることである。例えば、このポリパラキシリレン膜はベンゼン核の置換基の有無、置換基の種類によって多少相違するが空気中２００℃、約３０分以内で膜としての柔軟性や強度を無くし、軽く擦るだけでボロボロになる。この対策として酸化防止剤を混入する提案がなされているが本質的解決にならない（米国特許４，１７６，２０９、米国特許５，２６７，３９０および米国特許５，２７０，０８２参照）。
【０００６】
【発明が解決しようとする問題点】
ポリ−ｐ−キシリレン膜の更なる応用範囲拡大のためには酸素存在下における膜の耐熱性を高める必要がある。
ポリパラキシリレンのメチレン基の水素を全部フッ素で置き換えた下記構造
【化５】
【０００７】
本発明は、ポリ−ｐ−キシリレン膜の更なる応用範囲拡大のため、酸素存在下における膜の耐熱性を高めるとともに、その他の物性面すべてにバランスがとれたポリ−ｐ−キシリレン膜を形成するために有用な新規な化合物、テトラフルオロ−［２，２］−パラシクロファンを提供することを目的とする。
【０００８】
【課題を解決するための手段】
本発明者は、下記の反応式に示されるように、従来のポリパラキシリレン構造（ＩＶ）を、一方のメチレン基の水素二個をフッ素原子で置換した構造式Ｖ（ｎは重合度を示す。）に変えることで空気中での耐熱性あるポリマーとすることを意図し、そのポリマー製造のための出発原料としてテトラフルオロ−［２，２］−パラシクロファン（構造式Ｉ）の合成および化学蒸着法によるその重合を試みた。
【０００９】
【化６】
すなわち、本発明は上記構造式（Ｉ）でで表されるテトラフルオロ−［２，２］−パラシクロファンおよびその製造方法である。この物質の合成および化学蒸着はいまだ試みられたことはない。
この物質は一つの方法として次のルートで合成した。
【００１１】
【化７】
出発物質である［２，２］−パラシクロファン（構造式ＶＩ）は第３化成（株）から市販されている。
【００１３】
テトラブロモ−［２，２］−パラシクロファン（構造式ＶＩＩ）は［２，２］−パラシクロファン（構造式ＶＩ）を不活性溶剤中、過酸化物触媒の存在下、紫外線照射下、あるいは両者作用のもと、Ｎ−ブロムこはく酸イミドなどのブロム化剤と反応することで得られる。ブロム化では目的物の外に、構造式（ＶＩＩＩ）で示すブロム体も生成するが、溶媒に対する溶解度の差で分離することができる。
【００１４】
【化８】
ジケトン−［２，２］−パラシクロファン（構造式ＩＩ）はテトラブロモ−［２，２］−パラシクロファンに酢酸溶媒中で酢酸ソーダ、酢酸銀などを作用させる等の手段で合成できる。
目的物であるテトラフルオロ−［２，２］−パラシクロファン（構造式Ｉ）は上記ケトン体に四フッ化イオウあるいはジエチルアミノ硫黄トリフルオリド（以下、ＤＡＳＴと表示する。）などのフッ素化剤を作用して製造することができた。
【００１６】
テトラフルオロ−［２，２］−パラシクロファン（構造式Ｉ）の化学蒸着は［２，２］−パラシクロファンおよびその誘導体（構造式ＩＩＩ）に一般的に適用される条件で行ない、本物質のラジカルへの分解、その重合、成膜を試みた。
【００１７】
【実施例】
以下に実施例を示し、かつ本発明の物質により形成された膜の耐熱性試験の結果を記載する。本発明は実施例により限定されるものではない。
【００１８】
実施例１
（テトラブロモ−［２，２］−パラシクロファンの合成）
［２，２］−パラシクロファン４０．０ｇ、Ｎ−ブロモこはく酸イミド１６０．０ｇ及び過酸化ベンゾイル１．１ｇを四塩化炭素溶媒１．５１中で紫外線を照射しながら５０時間還流、反応した。熱時、不溶物濾過、四塩化炭素を蒸留回収、残留物をジクロロメタンで洗浄、さらにクロロホルムで再結晶してテトラブロモ−［２，２］−パラシクロファン（構造式ＶＩＩ）１４．４ｇを得た。（分解点：２２１〜２２３℃）
【００１９】
（ジケトン−［２，２］−パラシクロファンの合成）
上で合成したテトラブロム体１４．４ｇ、および酢酸銀１９．２ｇを酢酸２００ｍｌで４時間、還流下に反応、後に水１４ｍｌを加えさらに２時間、還流反応した。反応後、反応液を熱時濾過、酢酸を濃縮、水を加え析出した沈殿を濾取、炭酸カリ水溶液、さらに水で洗浄後、乾燥しジケトン−［２，２］−パラシクロファンを得た。収量５．７ｇ
【００２０】
（テトラフルオロ−［２，２］−パラシクロファンの合成）
上で合成したジケトン体５．７ｇ、ＤＡＳＴ９．５ｇをジクロロメタン中、３０℃以下で攪拌、２２時間反応した。水を加えて過剰のＤＡＳＴを分解、ジクロロメタン溶液を水、炭酸カリ水溶液、さらに水にて洗浄した。ジクロロメタンを留去、残留物をメタノールより再結晶し、テトラフルオロ−［２，２］−パラシクロファンを得た。収量４．９ｇ（融点：１９３〜１９５℃）。
構造は質量分析、核磁気共鳴分析などで確認した。
【００２１】
（化学蒸着法による重合膜の形成）
パラシクロファンおよびその誘導体（構造式ＩＩＩ）の一般的蒸着条件でガラス基板上へ蒸着を試みた。透明な薄膜の形成が認められた。
【００２２】
（ポリマーの熱安定性試験）
上記化学蒸着によりガラス基板上に生成した薄膜を基板上から剥取り熱安定性試験に供した。熱安定性試験は下記二つの方法にて行った。
（１）試料を２００℃に保った加熱炉の中に入れ、一定時間後、その膜の状態を調べる。
表１に構造式ＩＩＩからの膜と本発明品からの膜との耐熱性の比較を示す。
（２）示差熱分析により膜の分解発熱の認められる温度を測定し、比較する。
その結果を表２に示す。表２に記載の温度は発熱最大ピーク時の温度を示している。
【００２３】
【表１】
【表２】
【発明の効果】
ポリ−ｐ−キシリレン膜のさらなる応用範囲拡大のため、酸素存在下における膜の耐熱性を高めるとともに、その他の物性面すべてにバランスの期待できるコーティング膜生成のための新規化合物テトラフルオロ−［２，２］−パラシクロファンを提供することができる。本発明品の化学蒸着により生成する膜は従来品に比し、著しく耐熱性が向上し使用範囲の拡大を期待できる。[0001]
[Industrial application fields]
The present invention relates to a novel compound useful as a material for forming a coating film by chemical vapor deposition, tetrafluoro- [2,2] -paracyclophane, and a method for producing the same.
[0002]
[Prior art]
Structural formula (III)
[Chemical 3]
[0003]
[Formula 4]
With this coating method, a coating film can be formed on an object of any shape according to its shape. The polymer thin film thus formed has excellent gas barrier properties and dielectric properties, and can be used to coat electronic component materials or space equipment components. Widely used in
[0005]
However, the polyparaxylylene film from the above structural formula (III) has one limitation in use regardless of its excellent performance. In the polymer structure, the —CH 2 —CH 2 — structure linking the benzene nuclei is easily oxidized, so that it has a wide use range in vacuum and nitrogen, but the use temperature is limited in air. . For example, this polyparaxylylene film is slightly different depending on the presence or absence of substituents on the benzene nucleus and the type of substituents. However, the film does not have flexibility and strength within about 30 minutes at 200 ° C in air, and it can be rubbed lightly. Become tattered. As a countermeasure against this, proposals have been made to incorporate an antioxidant, but this is not an essential solution (see US Pat. No. 4,176,209, US Pat. No. 5,267,390 and US Pat. No. 5,270,082).
[0006]
[Problems to be solved by the invention]
In order to further expand the application range of the poly-p-xylylene film, it is necessary to improve the heat resistance of the film in the presence of oxygen.
The following structure in which all hydrogens of methylene group of polyparaxylylene are replaced with fluorine
[0007]
The present invention forms a poly-p-xylylene film in which the heat resistance of the film in the presence of oxygen is enhanced and all other physical properties are balanced in order to further expand the application range of the poly-p-xylylene film. It is an object of the present invention to provide a novel compound, tetrafluoro- [2,2] -paracyclophane useful for the purpose.
[0008]
[Means for Solving the Problems]
As shown in the following reaction formula, the present inventor has replaced the conventional polyparaxylylene structure (IV) with a structural formula V in which two hydrogen atoms of one methylene group are substituted with fluorine atoms (where n is the degree of polymerization). The synthesis of tetrafluoro- [2,2] -paracyclophane (Structural Formula I) is intended as a starting material for the production of the polymer. And its polymerization by chemical vapor deposition was tried.
[0009]
[Chemical 6]
That is, the present invention is tetrafluoro- [2,2] -paracyclophane represented by the structural formula (I) and a method for producing the same. The synthesis and chemical vapor deposition of this material has never been attempted.
This material was synthesized by the following route as one method.
[0011]
[Chemical 7]
The starting material [2,2] -paracyclophane (structure VI) is commercially available from Terumikasei Co., Ltd.
[0013]
Tetrabromo- [2,2] -paracyclophane (Structural Formula VII) is obtained by converting [2,2] -paracyclophane (Structural Formula VI) in an inert solvent, in the presence of a peroxide catalyst, under ultraviolet irradiation, or Under both actions, it can be obtained by reacting with a brominating agent such as N-bromosuccinimide. In the bromination, a bromide represented by the structural formula (VIII) is generated in addition to the target product, but can be separated by the difference in solubility in the solvent.
[0014]
[Chemical 8]
The diketone- [2,2] -paracyclophane (Structural Formula II) can be synthesized by means of reacting tetrabromo- [2,2] -paracyclophane with sodium acetate, silver acetate or the like in an acetic acid solvent.
The target product, tetrafluoro- [2,2] -paracyclophane (Structural Formula I), has a fluorinating agent such as sulfur tetrafluoride or diethylaminosulfur trifluoride (hereinafter referred to as DAST) on the ketone body. It was able to be produced by acting.
[0016]
Chemical vapor deposition of tetrafluoro- [2,2] -paracyclophane (Structural Formula I) is carried out under conditions generally applicable to [2,2] -paracyclophane and its derivatives (Structural Formula III). Attempts were made to decompose substances into radicals, polymerize them, and form films.
[0017]
【Example】
Examples are shown below, and the results of the heat resistance test of the film formed of the substance of the present invention are described. The present invention is not limited by the examples.
[0018]
Example 1
(Synthesis of tetrabromo- [2,2] -paracyclophane)
40.0 g of [2,2] -paracyclophane, 160.0 g of N-bromosuccinimide and 1.1 g of benzoyl peroxide were refluxed and reacted in a carbon tetrachloride solvent 1.51 while being irradiated with ultraviolet rays for 50 hours. . When heated, insoluble matters were filtered and carbon tetrachloride was recovered by distillation. The residue was washed with dichloromethane and further recrystallized with chloroform to obtain 14.4 g of tetrabromo- [2,2] -paracyclophane (Structural Formula VII). . (Decomposition point: 221 to 223 ° C.)
[0019]
(Synthesis of diketone- [2,2] -paracyclophane)
The tetrabromide synthesized above (14.4 g) and silver acetate (19.2 g) were reacted with 200 ml of acetic acid for 4 hours under reflux, and then 14 ml of water was added and refluxed for another 2 hours. After the reaction , the reaction solution was filtered while hot, acetic acid was concentrated, water was added, and the deposited precipitate was collected by filtration, washed with an aqueous potassium carbonate solution and further with water, and then dried to obtain diketone- [2,2] -paracyclophane. . Yield 5.7g
[0020]
(Synthesis of tetrafluoro- [2,2] -paracyclophane)
5.7 g of the diketone synthesized above and 9.5 g of DAST were reacted in dichloromethane at 30 ° C. or lower for 22 hours. Excess DAST was decomposed by adding water, and the dichloromethane solution was washed with water, an aqueous potassium carbonate solution, and further with water. Dichloromethane was distilled off and the residue was recrystallized from methanol to obtain tetrafluoro- [2,2] -paracyclophane. Yield 4.9 g (melting point: 193-195 ° C.).
The structure was confirmed by mass spectrometry and nuclear magnetic resonance analysis.
[0021]
(Formation of polymerized film by chemical vapor deposition)
Vapor deposition was attempted on a glass substrate under the general vapor deposition conditions of paracyclophane and its derivatives (structure III). Formation of a transparent thin film was observed.
[0022]
(Thermal stability test of polymer)
The thin film produced | generated on the glass substrate by the said chemical vapor deposition was peeled off from the board | substrate, and it used for the thermal stability test. The thermal stability test was conducted by the following two methods.
(1) The sample is placed in a heating furnace maintained at 200 ° C., and after a certain time, the state of the film is examined.
Table 1 shows a comparison of heat resistance between the film from Structural Formula III and the film from the product of the present invention.
(2) Measure and compare the temperature at which decomposition heat generation of the film is recognized by differential thermal analysis.
The results are shown in Table 2. The temperature described in Table 2 indicates the temperature at the maximum exothermic peak.
[0023]
[Table 1]
[Table 2]
【The invention's effect】
In order to further expand the application range of the poly-p-xylylene film, a novel compound tetrafluoro- [2, which increases the heat resistance of the film in the presence of oxygen and produces a coating film that can be balanced in all other physical properties. 2] -paracyclophane can be provided. The film produced by chemical vapor deposition of the product of the present invention is significantly improved in heat resistance and can be expected to expand the range of use compared to conventional products.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20896295A JP3771302B2 (en) | 1995-07-14 | 1995-07-14 | Tetrafluoro- [2,2] -paracyclophane and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20896295A JP3771302B2 (en) | 1995-07-14 | 1995-07-14 | Tetrafluoro- [2,2] -paracyclophane and process for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0925252A JPH0925252A (en) | 1997-01-28 |
| JP3771302B2 true JP3771302B2 (en) | 2006-04-26 |
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| JP20896295A Expired - Fee Related JP3771302B2 (en) | 1995-07-14 | 1995-07-14 | Tetrafluoro- [2,2] -paracyclophane and process for producing the same |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3773065B2 (en) * | 1995-08-25 | 2006-05-10 | 第三化成株式会社 | Dichloro-tetrafluoro- [2,2] -paracyclophane and process for producing the same |
| JP3595094B2 (en) * | 1997-01-14 | 2004-12-02 | 第三化成株式会社 | Heat resistant poly-α, α-difluoro-paraxylylene film |
| JPH10263087A (en) * | 1997-03-25 | 1998-10-06 | Nippon Zeon Co Ltd | Catheter and manufacture thereof |
| JP2000003909A (en) * | 1998-06-15 | 2000-01-07 | Kishimoto Sangyo Co Ltd | Semiconductor device and insulating film for the device |
| US7763318B2 (en) | 2003-12-19 | 2010-07-27 | Daisankasei Co., Ltd. | Method for improving heat stability of polyparaxylylene and derivative film thereof and polyparaxylylene derivative |
| US7994372B2 (en) | 2005-10-31 | 2011-08-09 | Specialty Coating Systems, Inc. | Parylene variants and methods of synthesis and use |
| US7462750B2 (en) | 2005-10-31 | 2008-12-09 | Specialty Coating Systems, Inc. | Parylene variants and methods of synthesis and use |
| JPWO2007083522A1 (en) | 2006-01-18 | 2009-06-11 | 株式会社ネクスト２１ | Medical gel-forming composition, administration device for the composition, and drug release control carrier |
| US7652178B2 (en) | 2007-02-26 | 2010-01-26 | Specialty Coating Systems, Inc. | Perfluoroparacyclophane and methods of synthesis and use thereof |
| US8945307B2 (en) | 2009-12-23 | 2015-02-03 | Aeroquest Research Group Llc | Apparatus and method for vapor deposition of dielectric wire coating |
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1995
- 1995-07-14 JP JP20896295A patent/JP3771302B2/en not_active Expired - Fee Related
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