JP2513595B2 - Method of molecular weight fractionation of ladder type silicone resin - Google Patents
Method of molecular weight fractionation of ladder type silicone resinInfo
- Publication number
- JP2513595B2 JP2513595B2 JP25091284A JP25091284A JP2513595B2 JP 2513595 B2 JP2513595 B2 JP 2513595B2 JP 25091284 A JP25091284 A JP 25091284A JP 25091284 A JP25091284 A JP 25091284A JP 2513595 B2 JP2513595 B2 JP 2513595B2
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- solvent
- silylated
- silicone resin
- type silicone
- 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.)
- Expired - Lifetime
Links
Landscapes
- Silicon Polymers (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はラダー構造をもつシリル化シルセスキオキサ
ン系ポリマー（別称ラダー型シリコン樹脂）について特
定の分子量分布のポリマーを分別する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for separating a polymer having a specific molecular weight distribution from a silylated silsesquioxane-based polymer having a ladder structure (also called a ladder-type silicone resin).
発明者等は電子線レジストとしてシリル化したシルセ
スキオキサン系ポリマーが優れた解像性と感度を示すこ
とを見いだし、この使用を提案している。The inventors have found that silylated silsesquioxane polymers as electron beam resists have excellent resolution and sensitivity, and have proposed their use.
ここでポリメチルシルセスキオキサン，ポリフェニル
シルセスキオキサン，ポリフェニルメチルシルセスキオ
キサンなどのシルセスキオキサン系ポリマーの製法はポ
リメチルシルセスキオキサンを例にとるとメチルトリク
ロルシラン，メチルトリメトキシシランなどを低温で加
水分解して三官能モノマーを形成した後、重縮合反応を
行って高分子化するために分子量分布が非常に大きい。Here, the method for producing silsesquioxane-based polymers such as polymethylsilsesquioxane, polyphenylsilsesquioxane, and polyphenylmethylsilsesquioxane is methyltrichlorosilane, methyl Since trimethoxysilane or the like is hydrolyzed at low temperature to form a trifunctional monomer, a polycondensation reaction is performed to polymerize the compound, so that the molecular weight distribution is very large.
それ故、かかるシルセスキオキサン系ポリマーをシリ
ル化した後、そのまま電子線レジストとして使用すると
分子量の大小によって溶剤に対する溶解度に差があるた
めに解像性の劣ったレジストとなってしまう。Therefore, if such a silsesquioxane-based polymer is silylated and then used as it is as an electron beam resist, the resist has poor resolution because the solubility in a solvent varies depending on the molecular weight.
それ故に特定の分子量範囲の樹脂を分別して使用する
必要がある。Therefore, it is necessary to separate and use a resin having a specific molecular weight range.
本発明はシリル化シルセスキオキサン系ポリマーの分
子量分布を分別する新しい方法に関するものである。The present invention relates to a new method for fractionating the molecular weight distribution of silylated silsesquioxane-based polymers.
シリル化シルセスキオキサン系ポリマーの分子量分布
から特定な範囲のものを分別する方法として従来は例え
ば４メチル２ペンタノンなどの溶剤に溶解した後にアセ
トニトリルなどの非溶剤を添加することによって分子量
の大きなものから沈澱する現象を利用して分別を行って
いた。As a method for separating a silylated silsesquioxane-based polymer in a specific range from the molecular weight distribution, conventionally, a polymer having a large molecular weight is prepared by dissolving it in a solvent such as 4-methyl-2pentanone and then adding a non-solvent such as acetonitrile. Separation was carried out by utilizing the phenomenon of sedimentation.
然し、この方法による場合は非溶剤の添加量や温度が
大きく影響するために所望の分子量組成のものを再現性
よく分別することができないと云う問題があり、再現性
よく分取する方法が要望されていた。However, when this method is used, there is a problem that it is not possible to reproducibly separate the desired molecular weight composition because the addition amount of the non-solvent and the temperature have a great influence, and a method for separating with good reproducibility is desired. It had been.
以上記したように広い分子量分布を持つシリル化シル
セスキオキサン系ポリマーから特定の分子量分布領域だ
けを分取する良い方法が見当たらないことが問題であ
る。As described above, the problem is that no good method for separating only a specific molecular weight distribution region from a silylated silsesquioxane-based polymer having a wide molecular weight distribution has been found.
上記の問題点はシリル化シルセスキオキサン系ポリマ
ーを溶解する各種溶剤について予め該溶剤とこれが可溶
する平均分子量の最大値との関係を求めておき、まず分
別する最大平均分子量を可溶限とする溶剤を用いて必要
とする平均分子量以下の樹脂溶液を作り、次に該溶液に
分別する最小平均分子量を可溶限とする溶剤を添加する
ことにより分別範囲の樹脂を沈澱せしめて分離すること
を特徴とするラダー型シリコン樹脂の分子量分別法の使
用により解決することができる。The above problem is that the relationship between the solvent and the maximum value of the average molecular weight in which the silylated silsesquioxane-based polymer is dissolved is determined in advance for each type of solvent in which the silylated silsesquioxane-based polymer is dissolved. A resin solution having a required average molecular weight or less is prepared by using a solvent, and then a solvent having a solubility limit of the minimum average molecular weight to be fractionated is added to the solution to precipitate and separate the resin in the fractionation range. The problem can be solved by using the molecular weight fractionation method of the ladder type silicone resin, which is characterized in that
シルセスキオキサン系ポリマーの溶剤に対する溶解度
はこのポリマーの分子量と、このポリマーが持つシラノ
ール基（Si−OH）の数に依存するが、発明者はシルセス
キオキサンに残るシラノール基（Si−OH）をシリル化
（−SiR3）してシラノール基（Si−OH）基による溶解因
子を除去した場合について溶剤に対する溶解性を調査し
た結果、溶解性が分子量に依存して明瞭に変化すること
を見いだした。The solubility of the silsesquioxane-based polymer in a solvent depends on the molecular weight of this polymer and the number of silanol groups (Si-OH) possessed by this polymer. ) Was silylated (-SiR 3 ) to remove the solubility factor due to the silanol group (Si-OH) group, and the solubility in solvent was investigated, and it was found that the solubility clearly changes depending on the molecular weight. I found it.
すなわち溶剤には溶質に対して弱く作用する溶剤と強
く作用する溶剤とがあるが、溶剤によってこれが可溶す
るシルセスキオキサン系ポリマーの最大平均分子量値が
明瞭に異なることを見いだした。That is, although there are some solvents that act weakly on the solute and those that strongly act on the solute, it was found that the maximum average molecular weight value of the silsesquioxane-based polymer in which the solute is soluble is clearly different depending on the solvent.
表は各溶剤による可溶限を溶剤の強弱の順に示すもの
である。The table shows the solubility limit of each solvent in order of strength and weakness of the solvent.
すなわち本発明はシリル化シルセスキオキサン系ポリ
マーから例えば１〜５×104の分子量成分を分別したい
場合は広い分子量分布をもつ樹脂よりイソプロパノール
を用いてMwが５×104までの成分を抽出した後に、メタ
ノールを添加してゆくとMwが１×104を越す成分は沈澱
してくるためにこれを回収することによって再現性よく
分別を行うものである。 That is, according to the present invention, when it is desired to separate, for example, a molecular weight component of 1 to 5 × 10 4 from a silylated silsesquioxane-based polymer, a component having a wide molecular weight distribution is used to extract components having an Mw of 5 × 10 4 using isopropanol. After that, when methanol is added, a component having an Mw of more than 1 × 10 4 is precipitated, so that the component is collected with good reproducibility for collection.
以下ラダー型シリコン樹脂としてシリル化ポリメチル
シルセスキオキサンの製法とこの方法で得られた広い分
子量分布の樹脂成分の中から特定の分子量成分を分別す
る方法を実施例について説明する。Hereinafter, a method for producing silylated polymethylsilsesquioxane as a ladder-type silicone resin and a method for separating a specific molecular weight component from the resin components having a wide molecular weight distribution obtained by this method will be described with reference to Examples.
ポリメチルシルセスキオキサンの合成例： ４メチル−２−ヘンタノン250gとトリエチルアミン3
1.2gとを１の丸底フラスコに入れ、ドライアイス−エ
タノール浴にて−20℃に冷却した。Synthesis example of polymethylsilsesquioxane: 250 g of 4-methyl-2-hentanone and triethylamine 3
1.2 g and 1 were put in a round bottom flask and cooled to -20 ° C in a dry ice-ethanol bath.
次にこれを撹拌しながら45gのメチルトリクロロシラ
ン、次いで54gの脱イオン水を滴下した。Then 45 g of methyltrichlorosilane were added dropwise with stirring, followed by 54 g of deionized water.
滴下終了後に混合液を徐々に室温にまで上昇した後、
95℃の温度で４時間に互って反応させた。After the dropping was completed, the mixture was gradually warmed to room temperature,
The reaction was continued for 4 hours at a temperature of 95 ° C.
このとき窒素ガス（N2）をバブリングして系内の塩素
ガス（Cl2）を系外に除去した。At this time, nitrogen gas (N 2 ) was bubbled to remove chlorine gas (Cl 2 ) in the system outside the system.
反応の終了後、１の脱イオン水で５回洗滌を行い有
機層を分取した。After completion of the reaction, the organic layer was separated by washing 5 times with 1 of deionized water.
次にシリル化の方法としてはこのようにして得られた
有機層に50gのトリメチルクロルシランを添加し、撹拌
しながら脱水ピリジン50gを滴下した。Next, as the silylation method, 50 g of trimethylchlorosilane was added to the organic layer thus obtained, and 50 g of dehydrated pyridine was added dropwise with stirring.
この反応液は１の脱イオン水を用いて５回洗滌し、
有機層を分取した。The reaction solution was washed 5 times with 1 deionized water,
The organic layer was separated.
これに500ccのアセトニトリルを添加し、生じた沈澱
を吸引濾過して乾燥し、シリル化ポリメチルシルセスキ
オキサンを得た。To this, 500 cc of acetonitrile was added, and the resulting precipitate was suction filtered and dried to obtain silylated polymethylsilsesquioxane.
この樹脂をGPC分析法で調べた結果、重量平均分子量
（Mw）は８×104であり、分散度（Mw/Mn）は6.5であっ
た。As a result of examining this resin by GPC analysis, the weight average molecular weight (Mw) was 8 × 10 4 , and the dispersity (Mw / Mn) was 6.5.
実施例1: このようにして合成したシリル化ポリメチルシルセス
キオキサン10gを200ccのイソプロパノールに溶解し、60
℃で20分間に互って加熱した後、20℃にて24時間静置し
た。Example 1: 10 g of the silylated polymethylsilsesquioxane thus synthesized was dissolved in 200 cc of isopropanol,
After heating at 20 ° C for 20 minutes, the mixture was allowed to stand at 20 ° C for 24 hours.
次に傾斜法により不溶解分を除去したのち、溶液を50
0ccのアセトニトリルに投入し、沈澱を吸引濾過して乾
燥した。Next, after removing the insoluble matter by the gradient method,
The mixture was added to 0 cc of acetonitrile, and the precipitate was suction filtered and dried.
この場合のMwは５×104であり、また分散度は1.8であ
った。In this case, Mw was 5 × 10 4 , and the dispersity was 1.8.
実施例2: 先の方法により合成したシリル化ポリメチルシルセス
キオキサン10gを200ccのシクロヘキサノンに溶解し、60
℃で20分に互って加熱した後、20℃で24時間静置した。Example 2: 10 g of silylated polymethylsilsesquioxane synthesized by the above method was dissolved in 200 cc of cyclohexanone,
After heating at 20 ° C. for 20 minutes, the mixture was allowed to stand at 20 ° C. for 24 hours.
次に傾斜法により不溶解成分を除去した後、１のイ
ソプロパノールを添加し、生じた沈澱を吸引濾過して乾
燥した。Then, insoluble components were removed by decantation, 1 isopropanol was added, and the resulting precipitate was suction filtered and dried.
このようにして得た樹脂のMwは13×104であり、また
分散度は2.3であった。The Mw of the resin thus obtained was 13 × 10 4 , and the dispersity was 2.3.
以上記したように本発明はシリル化シルセスキオキサ
ンが溶剤に対して明瞭な溶解特性を持つことを利用し、
強弱二つの溶剤を用いて特定の分子量分布の樹脂を分別
するもので、本発明の実施により再現性の良い分取が可
能になる。As described above, the present invention utilizes the fact that silylated silsesquioxane has a clear solubility property in a solvent,
A resin having a specific molecular weight distribution is separated using two strong and weak solvents, and the practice of the present invention enables the separation with good reproducibility.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 西井 耕太 川崎市中原区上小田中1015番地 富士通 株式会社内 (72)発明者 松浦 東 川崎市中原区上小田中1015番地 富士通 株式会社内 (56)参考文献 特開 昭57−10627（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kota Nishii, 1015 Kamiodanaka, Nakahara-ku, Kawasaki-shi, inside Fujitsu Limited (72) Inventor Matsuura Higashi, 1015 Kamikotanaka, Nakahara-ku, Kawasaki, inside Fujitsu Limited (56) References JP-A-57-10627 (JP, A)
Claims (1)
溶解する各種溶剤について予め該溶剤とこれが可溶する
平均分子量の最大値との関係を求めておき、まず分別す
る最大平均分子量を可溶限とする溶剤を用いて必要とす
る平均分子量以下の樹脂溶液を作り、次に該溶液に分別
する最小平均分子量を可溶限とする溶剤を添加すること
により分別範囲の樹脂を沈澱せしめて分離することを特
徴とするラダー型シリコン樹脂の分子量分別法。1. A relationship between the solvent and the maximum value of the average molecular weight in which the silylated silsesquioxane-based polymer is dissolved is obtained in advance, and the maximum average molecular weight to be fractionated is first determined by the solubility limit. A resin solution having a required average molecular weight or less is prepared by using a solvent, and then a solvent having a solubility limit of the minimum average molecular weight to be fractionated is added to the solution to precipitate and separate the resin in the fractionation range. A method for separating molecular weight of ladder-type silicone resin, which is characterized in that
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25091284A JP2513595B2 (en) | 1984-11-28 | 1984-11-28 | Method of molecular weight fractionation of ladder type silicone resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25091284A JP2513595B2 (en) | 1984-11-28 | 1984-11-28 | Method of molecular weight fractionation of ladder type silicone resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61127732A JPS61127732A (en) | 1986-06-16 |
| JP2513595B2 true JP2513595B2 (en) | 1996-07-03 |
Family
ID=17214869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25091284A Expired - Lifetime JP2513595B2 (en) | 1984-11-28 | 1984-11-28 | Method of molecular weight fractionation of ladder type silicone resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2513595B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5063267A (en) * | 1990-11-28 | 1991-11-05 | Dow Corning Corporation | Hydrogen silsesquioxane resin fractions and their use as coating materials |
| JPH0539357A (en) * | 1991-08-06 | 1993-02-19 | Toray Dow Corning Silicone Co Ltd | Phenylpolysilsesquioxane and its production |
| JP3153367B2 (en) * | 1992-11-24 | 2001-04-09 | ダウ・コ−ニング・コ−ポレ−ション | Molecular weight fractionation method for polyhydrogensilsesquioxane |
| US5779299A (en) * | 1995-06-07 | 1998-07-14 | Asc Incorporated | Apparatus for achieving automotive vehicle roof isolation |
-
1984
- 1984-11-28 JP JP25091284A patent/JP2513595B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61127732A (en) | 1986-06-16 |
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