JPH06306175A - Fluorine-containing hydrogensilsesquioxane polymer - Google Patents
Fluorine-containing hydrogensilsesquioxane polymerInfo
- Publication number
- JPH06306175A JPH06306175A JP5247473A JP24747393A JPH06306175A JP H06306175 A JPH06306175 A JP H06306175A JP 5247473 A JP5247473 A JP 5247473A JP 24747393 A JP24747393 A JP 24747393A JP H06306175 A JPH06306175 A JP H06306175A
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- Prior art keywords
- polymer
- formula
- fluorine
- repeating unit
- acid
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は新規な弗素含有水素シル
セスキオキサンポリマーに関する。FIELD OF THE INVENTION The present invention relates to a novel fluorine-containing hydrogen silsesquioxane polymer.
【０００２】[0002]
【従来の技術】ラダー構造を有する水素シルセスキオキ
サンポリマーは分子量や側鎖の種類などにより油状、樹
脂状と幅広い性状を示す。その特徴である有機溶媒可溶
性、酸化安定性、耐熱性、耐寒性、耐候性などを利用し
て、接着剤分野、電気・電子材料分野、塗料分野など多
岐の工業分野で使用されている。2. Description of the Related Art Hydrogen silsesquioxane polymers having a ladder structure show a wide range of properties such as oily and resinous properties depending on the molecular weight and the type of side chain. It is used in various industrial fields such as adhesives field, electric / electronic materials field, and paint field by utilizing its characteristics such as organic solvent solubility, oxidation stability, heat resistance, cold resistance, and weather resistance.
【０００３】[0003]
【発明が解決しようとする課題】本発明者らは新規な水
素シルセスキオキサンポリマーを開発すべく鋭意研究の
結果、後記式（４）、（５）及び（６）から選ばれる繰
り返し単位を有し、ポリマー中の弗素含有量が０．２〜
２０重量％であるポリマーは新規ポリマーであり、弗素
を含有しない水素シルセスキオキサンポリマーと比較し
て、比誘電率が低いことを見出し、この知見に基づいて
本発明を完成するに到った。DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of intensive research to develop a novel hydrogen silsesquioxane polymer, the present inventors have found that a repeating unit selected from the following formulas (4), (5) and (6) is used. And the fluorine content in the polymer is 0.2 to
The polymer of 20% by weight is a novel polymer and was found to have a lower relative dielectric constant as compared with a hydrogen silsesquioxane polymer containing no fluorine, and the present invention was completed based on this finding. .
【０００４】[0004]
【課題を解決する為の手段】かくして本発明によれば式
（４）、（５）及び（６）から選ばれる繰り返し単位を
有し（但し、繰り返し単位が式（４）のみ、または式
（６）のみである場合を除く。）、ポリマー中の弗素含
有量が０．２〜２０．０重量％であることを特徴とする
弗素含有水素シルセスキオキサンポリマーが提供され
る。According to the present invention, there is thus a repeating unit selected from the formulas (4), (5) and (6) (provided that the repeating unit is the formula (4) alone or the formula (4) 6) only)), and a fluorine-containing hydrogen silsesquioxane polymer having a fluorine content in the polymer of 0.2 to 20.0% by weight.
【０００５】[0005]
【化４】 [Chemical 4]
【化５】 [Chemical 5]
【化６】 [Chemical 6]
【０００６】本発明の弗素含有水素シルセスキオキサン
ポリマーは文献未記載の新規なポリマーである。かかる
弗素含有水素シルセスキオキサンポリマーの製造方法と
しては、例えば、下記式（７）で表される弗素化シラン
化合物を、または前記弗素化シラン化合物と下記式
（８）で表されシラン化合物との混合物を、硫酸とアリ
ールスルホン酸水和物からなる加水分解媒体中で分解縮
合させる方法が挙げられる。The fluorine-containing hydrogen silsesquioxane polymer of the present invention is a novel polymer not described in the literature. As a method for producing such a fluorine-containing hydrogen silsesquioxane polymer, for example, a fluorinated silane compound represented by the following formula (7) or a silane compound represented by the following formula (8) is used. A method of decomposing and condensing the mixture of 1) in a hydrolysis medium composed of sulfuric acid and arylsulfonic acid hydrate.
【０００７】[0007]
【化７】 （式中、Ｘは加水分解性基を示す。）[Chemical 7] (In the formula, X represents a hydrolyzable group.)
【化８】 （式中、Ｙは加水分解性基を示す。）[Chemical 8] (In the formula, Y represents a hydrolyzable group.)
【０００８】Ｘ及びＹは加水分解性基であり、具体的に
は塩素、臭素、ヨウ素などのハロゲン原子；メトキシ
基、エトキシ基、プロポキシ基、ブトキシ基などのアル
コキシ基；アリルオキシ基のようなアルケニルオキシ
基；フェノキシ基、ナフトキシ基などのアリールオキシ
基；シクロペンテニルオキシ基のようなシクロアルケニ
ルオキシ基；ホルミル基、アセトキシ基、プロピオニル
オキシ基などのアシルオキシ基などが挙げられる。なか
でもハロゲン原子が賞用される。X and Y are hydrolyzable groups, specifically, halogen atoms such as chlorine, bromine and iodine; alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group; alkenyl such as allyloxy group. Examples thereof include an oxy group; an aryloxy group such as a phenoxy group and a naphthoxy group; a cycloalkenyloxy group such as a cyclopentenyloxy group; and an acyloxy group such as a formyl group, an acetoxy group and a propionyloxy group. Among them, halogen atoms are prized.
【０００９】混合物の場合は式（７）で表される弗素化
シラン化合物１モルに対し、式（８）で表されるシラン
化合物が、通常、１〜９９モル、好ましくは１〜５０モ
ル、さらに好ましくは３〜３０モルの範囲で用いられ
る。加水分解媒体のアリールスルホン酸の水和物として
はベンゼンスルホン酸、トルエンスルホン酸、キシレン
スルホン酸などの水和物が例示される。分解縮合反応
は、通常、０〜５０℃、１〜１０時間で行われる。分解
縮合反応に関するその他の条件は特に限定されないが、
通常は、攪拌下に実施するのが好ましい。また、圧力は
減圧または加圧の何れでも構わない。In the case of a mixture, the silane compound represented by the formula (8) is usually 1 to 99 mol, preferably 1 to 50 mol, relative to 1 mol of the fluorinated silane compound represented by the formula (7). It is more preferably used in the range of 3 to 30 mol. Examples of the hydrate of arylsulfonic acid as the hydrolysis medium include hydrates of benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid and the like. The decomposition condensation reaction is usually performed at 0 to 50 ° C. for 1 to 10 hours. Other conditions for the decomposition condensation reaction are not particularly limited,
Usually, it is preferable to carry out the reaction under stirring. The pressure may be reduced pressure or increased pressure.
【００１０】本発明の弗素含有水素シルセスキオキサン
ポリマー中の弗素含有量は０．２〜２０重量％、好まし
くは０．４〜１５重量％、さらに好ましくは１．５〜１
０重量％である。また、弗素含有水素シルセスキオキサ
ンポリマーの重量平均分子量（ゲルパーミェーションク
ロマトグラフィーにより標準ポリスチレンに換算して求
めた分子量）は、１，０００〜１，０００，０００、好
ましくは２，０００〜１００，０００、さらに好ましく
は２，０００〜５０，０００である。The fluorine content in the fluorine-containing hydrogen silsesquioxane polymer of the present invention is 0.2 to 20% by weight, preferably 0.4 to 15% by weight, more preferably 1.5 to 1%.
It is 0% by weight. The weight average molecular weight of the fluorine-containing hydrogen silsesquioxane polymer (the molecular weight obtained by converting it into standard polystyrene by gel permeation chromatography) is 1,000 to 1,000,000, preferably 2,000. 100 to 100,000, more preferably 2,000 to 50,000.
【００１１】かくして本発明で得られた弗素含有水素シ
ルセスキオキサンポリマーは比誘電率が低いため、電気
・電子材料分野における用途が期待できる。Thus, the fluorine-containing hydrogen silsesquioxane polymer obtained by the present invention has a low relative permittivity, and thus can be expected to be used in the field of electric / electronic materials.
【００１２】[0012]
【実施例】以下に実施例を挙げて本発明をさらに具体的
に説明する。なお、実施例及び比較例中の部及び％は特
に断りのないかぎり重量基準である。EXAMPLES The present invention will be described in more detail with reference to the following examples. Parts and% in the examples and comparative examples are based on weight unless otherwise specified.
【００１３】実施例１ ９５％硫酸１３０グラムと発煙硫酸（６０％ＳＯ3）４
８グラムとを反応器に入れ、攪拌下にトルエン１５０グ
ラムを３０分で滴下し、ｐ−トルエンスルホン酸を合成
した。次に、攪拌下、２０℃で、６００ミリリットルの
トルエンで希釈したフロオロトリクロロシラン４．９グ
ラムとトリクロロシラン５７．９グラムを４時間かけて
滴下し、さらに３０分間攪拌を続けた。有機層と酸層と
を分離し、有機層を５０％濃度の硫酸で洗浄した後、濾
液を炭酸カルシウムで中和後、硫酸マグネシウムで乾燥
し、溶媒を留去したところ、弗素含有水素シルセスキオ
キサンポリマーが２３．６グラム（収率９６．６％）得
られた。ポリマーの重量平均分子量（ゲルパーミェーシ
ョンクロマトグラフィーにより標準ポリスチレンに換算
して求めた分子量）は５４４０であった。Example 1 130 grams of 95% sulfuric acid and 4% fuming sulfuric acid (60% SO 3 )
Then, 8 g and 150 g of toluene were added dropwise to the reactor under stirring for 30 minutes to synthesize p-toluenesulfonic acid. Next, under stirring, at 20 ° C., 4.9 g of fluorotrichlorosilane and 57.9 g of trichlorosilane diluted with 600 ml of toluene were added dropwise over 4 hours, and stirring was continued for another 30 minutes. The organic layer and the acid layer were separated, the organic layer was washed with 50% sulfuric acid, the filtrate was neutralized with calcium carbonate and dried over magnesium sulfate, and the solvent was distilled off. 23.6 g (yield 96.6%) of oxane polymer was obtained. The weight average molecular weight of the polymer (molecular weight obtained by converting to standard polystyrene by gel permeation chromatography) was 5,440.
【００１４】弗素含有水素シルセスキオキサンポリマー
の物性値を以下に示す。 ＩＲ（ＫＢｒ）：１０８０ｃｍ-1及び１１２０ｃｍ-1に
ラダーポリマーに特徴的なＳｉ−Ｏ−Ｓｉの収縮振動が
見られた。９４０ｃｍ-1にＳｉ−Ｆの吸収が、２２６０
ｃｍ-1にＳｉ−Ｈの吸収が観察された。 ４７０ＭＨｚ 19ＦＮＭＲ（ＦＣＣｌ3）：１４８．４
ｐｐｍ、１５０ｐｐｍ及び１５２ｐｐｍにＯ−Ｓｉ−Ｆ
に帰属するシグナルが観察された。 Ｘ線光電子分光分析により組成を求めたところＨ0.90Ｆ
0.10Ｓｉ1.00Ｏ1.52（理論値Ｈ0.93Ｆ0.07Ｓｉ1.00Ｏ
1.50）であった。The physical properties of the fluorine-containing hydrogen silsesquioxane polymer are shown below. IR (KBr): At 1080 cm −1 and 1120 cm −1 , contraction vibration of Si—O—Si characteristic of the ladder polymer was observed. Absorption of Si-F at 940 cm -1 is 2260
Absorption of Si-H was observed at cm- 1 . 470 MHz 19 F NMR (FCCl 3 ): 148.4
O-Si-F at ppm, 150 ppm and 152 ppm
A signal attributed to was observed. When the composition was determined by X-ray photoelectron spectroscopy analysis, H 0.90 F
0.10 Si 1.00 O 1.52 (Theoretical value H 0.93 F 0.07 Si 1.00 O
1.50 ).
【００１５】また、弗素含有水素シルセスキオキサンポ
リマーを用いて作製した酸化膜について１０ＫＨｚの容
量・電圧特性から求めた比誘電率は３．５であった。比
較のためトリクロロシランをモノマーとして同様に分解
縮合させて得た水素シルセスキオキサンポリマーについ
て比誘電率を求めたところ４．０であった。Further, the relative dielectric constant of the oxide film produced using the fluorine-containing hydrogen silsesquioxane polymer was 3.5, which was obtained from the capacity / voltage characteristics at 10 KHz. For comparison, the relative dielectric constant of the hydrogen silsesquioxane polymer obtained by decomposing and condensing trichlorosilane as a monomer was 4.0.
【００１６】実施例２ ６００ミリリットルのトルエンで希釈したフロロトリク
ロロシラン１４．５グラムとトリクロロシラン５０．９
グラムを用いること以外は実施例１に準じて操作を行っ
たところ、弗素含有水素シルセスキオキサンポリマーが
２５．０グラム（収率９９．１％）得られた。ポリマー
の重量平均分子量（ゲルパーミェーションクロマトグラ
フィーにより標準ポリスチレンに換算して求めた分子
量）は９０８０であった。Example 2 14.5 grams of fluorotrichlorosilane and 50.9 trichlorosilane diluted in 600 milliliters of toluene.
The operation was carried out in the same manner as in Example 1 except that gram was used, whereby 25.0 g (yield 99.1%) of a fluorine-containing hydrogen silsesquioxane polymer was obtained. The weight average molecular weight of the polymer (molecular weight obtained by converting to standard polystyrene by gel permeation chromatography) was 9080.
【００１７】弗素含有水素シルセスキオキサンポリマー
の物性値を以下に示す。 ＩＲ（ＫＢｒ）：１０８０ｃｍ-1及び１１２０ｃｍ-1に
ラダーポリマーに特徴的なＳｉ−Ｏ−Ｓｉの収縮振動が
見られた。９４０ｃｍ-1にＳｉ−Ｆの吸収が、２２６０
ｃｍ-1にＳｉ−Ｈの吸収が観察された。 ４７０ＭＨｚ 19ＦＮＭＲ（ＦＣＣｌ3）：１４８．４
ｐｐｍ、１５０ｐｐｍ及び１５２ｐｐｍにＯ−Ｓｉ−Ｆ
に帰属するシグナルが観察された。 Ｘ線光電子分光分析により組成を求めたところＨ0.71Ｆ
0.29Ｓｉ1.00Ｏ1.52（理論値Ｈ0.77Ｆ0.23Ｓｉ1.00Ｏ
1.50）であった。また、弗素含有水素シルセスキオキサ
ンポリマーを用いて作製した酸化膜について１０ＫＨｚ
の容量・電圧特性から求めた比誘電率は３．４であっ
た。The physical properties of the fluorine-containing hydrogen silsesquioxane polymer are shown below. IR (KBr): At 1080 cm −1 and 1120 cm −1 , contraction vibration of Si—O—Si characteristic of the ladder polymer was observed. Absorption of Si-F at 940 cm -1 is 2260
Absorption of Si-H was observed at cm- 1 . 470 MHz 19 F NMR (FCCl 3 ): 148.4
O-Si-F at ppm, 150 ppm and 152 ppm
A signal attributed to was observed. When the composition was determined by X-ray photoelectron spectroscopy analysis, it was H 0.71 F
0.29 Si 1.00 O 1.52 (Theoretical value H 0.77 F 0.23 Si 1.00 O
1.50 ). In addition, for an oxide film formed using a fluorine-containing hydrogen silsesquioxane polymer, 10 kHz
The relative permittivity calculated from the capacity / voltage characteristics of was 3.4.
【００１８】実施例３ ６００ミリリットルのトルエンで希釈したフロロトリク
ロロシラン８．８５グラムとトリクロロシラン５４．８
グラムを用いること以外は実施例１に準じて操作を行っ
たところ、弗素含有水素シルセスキオキサンポリマーが
２４．６グラム（収率９９．８％）得られた。ポリマー
の重量平均分子量（ゲルパーミェーションクロマトグラ
フィーにより標準ポリスチレンに換算して求めた分子
量）は６６００であった。Example 3 8.85 grams of fluorotrichlorosilane and 54.8 trichlorosilane diluted in 600 milliliters of toluene.
The procedure of Example 1 was repeated, except that the amount of gram was changed, to obtain 24.6 g of fluorine-containing hydrogen silsesquioxane polymer (yield: 99.8%). The weight average molecular weight of the polymer (molecular weight obtained by converting to standard polystyrene by gel permeation chromatography) was 6,600.
【００１９】弗素含有水素シルセスキオキサンポリマー
の物性値を以下に示す。 ＩＲ（ＫＢｒ）：１０８０ｃｍ-1及び１１２０ｃｍ-1に
ラダーポリマーに特徴的なＳｉ−Ｏ−Ｓｉの収縮振動が
見られた。９４０ｃｍ-1にＳｉ−Ｆの吸収が、２２６０
ｃｍ-1にＳｉ−Ｈの吸収が観察された。 ４７０ＭＨｚ 19ＦＮＭＲ（ＦＣＣｌ3）：１４８．４
ｐｐｍ、１５０ｐｐｍ及び１５２ｐｐｍにＯ−Ｓｉ−Ｆ
に帰属するシグナルが観察された。 Ｘ線光電子分光分析により組成を求めたところＨ0.85Ｆ
0.15Ｓｉ1.00Ｏ1.54（理論値Ｈ0.86Ｆ0.14Ｓｉ1.00Ｏ
1.50）であった。また、弗素含有水素シルセスキオキサ
ンポリマーを用いて作製した酸化膜について１０ＫＨｚ
の容量・電圧特性から求めた比誘電率は３．５であっ
た。The physical properties of the fluorine-containing hydrogen silsesquioxane polymer are shown below. IR (KBr): At 1080 cm −1 and 1120 cm −1 , contraction vibration of Si—O—Si characteristic of the ladder polymer was observed. Absorption of Si-F at 940 cm -1 is 2260
Absorption of Si-H was observed at cm- 1 . 470 MHz 19 F NMR (FCCl 3 ): 148.4
O-Si-F at ppm, 150 ppm and 152 ppm
A signal attributed to was observed. When the composition was determined by X-ray photoelectron spectroscopy analysis, it was H 0.85 F
0.15 Si 1.00 O 1.54 (Theoretical value H 0.86 F 0.14 Si 1.00 O
1.50 ). In addition, for an oxide film formed using a fluorine-containing hydrogen silsesquioxane polymer, 10 kHz
The relative permittivity calculated from the capacitance / voltage characteristics of was 3.5.
Claims (1)
繰り返し単位を有し（但し、繰り返し単位が式（１）の
み、または式（３）のみである場合を除く。）、ポリマ
ー中の弗素含有量が０．２〜２０．０重量％であること
を特徴とする弗素含有水素シルセスキオキサンポリマ
ー。 【化１】 【化２】 【化３】 1. A repeating unit selected from formulas (1), (2) and (3) (provided that the repeating unit is only formula (1) or formula (3)). A fluorine-containing hydrogen silsesquioxane polymer, wherein the fluorine content in the polymer is 0.2 to 20.0% by weight. [Chemical 1] [Chemical 2] [Chemical 3]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24747393A JP3465314B2 (en) | 1993-02-23 | 1993-09-08 | Fluorine-containing hydrogen silsesquioxane polymer and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5-56403 | 1993-02-23 | ||
| JP5640393 | 1993-02-23 | ||
| JP24747393A JP3465314B2 (en) | 1993-02-23 | 1993-09-08 | Fluorine-containing hydrogen silsesquioxane polymer and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06306175A true JPH06306175A (en) | 1994-11-01 |
| JP3465314B2 JP3465314B2 (en) | 2003-11-10 |
Family
ID=26397354
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24747393A Expired - Fee Related JP3465314B2 (en) | 1993-02-23 | 1993-09-08 | Fluorine-containing hydrogen silsesquioxane polymer and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3465314B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6440550B1 (en) * | 1999-10-18 | 2002-08-27 | Honeywell International Inc. | Deposition of fluorosilsesquioxane films |
| JP5500824B2 (en) * | 2006-09-13 | 2014-05-21 | 株式会社カネカ | Moisture curable polymer having SiF group and curable composition containing the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03217419A (en) * | 1990-01-24 | 1991-09-25 | Asahi Chem Ind Co Ltd | Siloxane compound and production thereof |
| JPH04216827A (en) * | 1990-02-22 | 1992-08-06 | Dow Corning Corp | Precursor polymer for ceramic coating |
| JPH05230215A (en) * | 1992-02-21 | 1993-09-07 | Showa Denko Kk | Fluoropolyorganosilsesquioxane and its production |
| JPH06157760A (en) * | 1992-11-24 | 1994-06-07 | Toray Dow Corning Silicone Co Ltd | Method for fractionating molecular weight of polyhydrogensilsesquioxane |
-
1993
- 1993-09-08 JP JP24747393A patent/JP3465314B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03217419A (en) * | 1990-01-24 | 1991-09-25 | Asahi Chem Ind Co Ltd | Siloxane compound and production thereof |
| JPH04216827A (en) * | 1990-02-22 | 1992-08-06 | Dow Corning Corp | Precursor polymer for ceramic coating |
| JPH05230215A (en) * | 1992-02-21 | 1993-09-07 | Showa Denko Kk | Fluoropolyorganosilsesquioxane and its production |
| JPH06157760A (en) * | 1992-11-24 | 1994-06-07 | Toray Dow Corning Silicone Co Ltd | Method for fractionating molecular weight of polyhydrogensilsesquioxane |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6440550B1 (en) * | 1999-10-18 | 2002-08-27 | Honeywell International Inc. | Deposition of fluorosilsesquioxane films |
| US6838124B2 (en) * | 1999-10-18 | 2005-01-04 | Honeywell International Inc. | Deposition of fluorosilsesquioxane films |
| JP5500824B2 (en) * | 2006-09-13 | 2014-05-21 | 株式会社カネカ | Moisture curable polymer having SiF group and curable composition containing the same |
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| JP3465314B2 (en) | 2003-11-10 |
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