JPH05125187A - Polyorganosilsesquioxane and its production - Google Patents
Polyorganosilsesquioxane and its productionInfo
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- JPH05125187A JPH05125187A JP22189891A JP22189891A JPH05125187A JP H05125187 A JPH05125187 A JP H05125187A JP 22189891 A JP22189891 A JP 22189891A JP 22189891 A JP22189891 A JP 22189891A JP H05125187 A JPH05125187 A JP H05125187A
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- polyorganosilsesquioxane
- molecular weight
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ラダー状分子構造を有
し、耐熱性、硬度、絶縁性等の面で、優れた特性を示す
超高分子量のポリオルガノシルセスキオキサン及びその
製造方法に関する。FIELD OF THE INVENTION The present invention relates to an ultrahigh molecular weight polyorganosilsesquioxane having a ladder-like molecular structure and exhibiting excellent properties in terms of heat resistance, hardness, insulation and the like, and a method for producing the same. Regarding
【０００２】[0002]
【従来の技術】宇宙開発に伴いポリイミドをはじめとす
る一群の高耐熱性樹脂が開発され、最近では電気、電子
産業分野における小型、軽量化、高性能化の要請に応え
るため、更に自動車産業の軽量化などの進展につれてそ
の市場が大幅に拡大され、耐熱樹脂に対する要望はます
ます増大していると共に、より一層の耐熱性の向上が求
められている。2. Description of the Related Art A group of highly heat-resistant resins such as polyimide has been developed with the development of space, and recently, in order to meet the demands for smaller size, lighter weight and higher performance in the fields of electric and electronic industries, further development of automobile industry With the progress of weight reduction and the like, the market has expanded significantly, and the demand for heat-resistant resins is increasing more and more, and further improvement in heat resistance is required.
【０００３】しかしながら、炭素骨格のプラスチックは
耐熱性の点では一定の限界がある事は止むを得ない事で
あり、その点では珪素骨格のプラスチック材料は一層高
度な性能を実現しうる可能性を秘めている。However, it is unavoidable that the carbon skeleton plastic has a certain limit in terms of heat resistance, and in that respect, the silicon skeleton plastic material has a possibility of realizing higher performance. I have a secret.
【０００４】ところで、ラダーシリコーンの略称で知ら
れるポリオルガノシルセスキオキサンは、シロキサン骨
格結合の分子の動きが固定されていてシリカ類似の骨格
構造を有しており、硬度、耐熱性等の目的に対しては理
想的な構造を有している。とりわけ側鎖がメチルのポリ
メチルシルセスキオキサンは分子構造上も特に無機的な
性質を示し硬度、耐熱性が高い。By the way, polyorganosilsesquioxane known by the abbreviation of ladder silicone has a siloxane skeleton-bonded molecule having a fixed movement and has a skeleton structure similar to silica, and has a purpose of hardness, heat resistance and the like. Has an ideal structure for. In particular, polymethylsilsesquioxane having a methyl side chain exhibits particularly inorganic properties in terms of molecular structure and has high hardness and heat resistance.
【０００５】しかしながら、上記のような側鎖の大部分
がメチル基であるポリオルガノシルセスキオキサンは合
成上多くの障害があって広く一般に使用されるには問題
があることも知られている。その理由の一つは、ポリメ
チルシルセスキオキサンは側鎖による立体障害が少な
く、末端基のシラノール及びアルコキシ基の反応性が高
いため、合成時や保存時にゲル化しやすいことが知られ
ている。このため高分子量のものはこれまで合成されて
おらず、オリゴマー領域のものが唯一製品化されている
にすぎない（商品名；グラスレジン 米国ＯＩ−ＮＥＧ
社）。However, it is also known that polyorganosilsesquioxanes having a majority of side chains as described above having a methyl group have many obstacles in their synthesis and are problematic in widespread use. .. One of the reasons is that polymethylsilsesquioxane has less steric hindrance due to side chains and the reactivity of silanol and alkoxy groups as terminal groups is high, and it is known that gelation easily occurs during synthesis or storage. .. For this reason, high molecular weight compounds have not been synthesized so far, and only oligomers have been commercialized (trade name; Glass Resin USA OI-NEG).
Company).
【０００６】上記のオリゴマーの溶液は例えば金属、プ
ラスチック等の基材にコーティングし、溶剤の揮発後加
熱すると末端基のシラノール基、アルコキシ基間での脱
水、脱アルコールを伴う縮合反応により三次元硬化する
ためコーティング被膜として用いられている。この被膜
は硬度、耐熱性は高いものの、極めてもろく、基材の大
きな変形には充分追随することができないことが第２の
問題点であり、従って実用的には数ミクロン程度の薄膜
としてのみ利用されている。The solution of the above oligomer is coated on a substrate such as metal or plastic, and when the solvent is volatilized and heated, dehydration between silanol groups and alkoxy groups of the terminal groups and three-dimensional curing by condensation reaction involving dealcoholization. Therefore, it is used as a coating film. Although this coating has high hardness and heat resistance, it is extremely brittle and cannot follow the large deformation of the base material, which is the second problem. Therefore, it is practically used only as a thin film of about several microns. Has been done.
【０００７】また、上述したように三次元硬化するに当
り、加熱硬化が不可欠であることが第３問題点であり、
実際には使用する基材によっては適用温度の制約があ
り、更に硬化に長時間を要することはコストとプロセス
面での難点を伴うことにもつながっている。A third problem is that heat curing is indispensable for three-dimensional curing as described above.
In practice, there are restrictions on the application temperature depending on the substrate used, and it takes a long time to cure, which also leads to problems in terms of cost and process.
【０００８】[0008]
【発明が解決しようとする課題】本発明は側鎖がメチル
基を主体とするポリオルガノシルセスキオキサンの上述
の問題点を解決する目的でなされたものであり、超高分
子量であって、加熱硬化をしなくても強靱さ、硬度、耐
熱性を示す新しいポリオルガノシルセスキオキサン及び
その製造方法を提供することを目的とする。The present invention has been made for the purpose of solving the above-mentioned problems of polyorganosilsesquioxane having a side chain mainly composed of a methyl group, and has an ultrahigh molecular weight, An object of the present invention is to provide a new polyorganosilsesquioxane exhibiting toughness, hardness, and heat resistance without heat curing and a method for producing the same.
【０００９】[0009]
【課題を解決するための手段】本発明者らは上記目的を
達成するため、鋭意検討を進めた結果、特定の骨格構造
と超高分子量を有するポリオルガノシルセスキオキサン
により上記目的が満たされることを見出し、本発明を完
成するに至った。すなわち本発明は一般式（Ｉ）で構造
が示されるポリオルガノシルセスキオキサンにおいて、
全側鎖Ｒ1 の５０〜１００モル％がメチル基であり、残
りの側鎖は炭素原子数２ないし３個のアルキル基か置換
または非置換フェニル基であり、数平均分子量が１０
０，０００以上であることを特徴とするポリオルガノシ
ルセスキオキサンに関する。Means for Solving the Problems The present inventors have conducted extensive studies to achieve the above object, and as a result, the above object is satisfied by a polyorganosilsesquioxane having a specific skeletal structure and an ultrahigh molecular weight. This has led to the completion of the present invention. That is, the present invention provides a polyorganosilsesquioxane represented by the general formula (I),
50 to 100 mol% of all side chains R 1 are methyl groups, the remaining side chains are alkyl groups having 2 to 3 carbon atoms or substituted or unsubstituted phenyl groups, and have a number average molecular weight of 10
The present invention relates to a polyorganosilsesquioxane having a content of 50,000 or more.
【００１０】[0010]
【化２】 [Chemical 2]
【００１１】〔一般式（Ｉ）において、Ｒ2 は炭素原子
数１ないし３個のアルキル基または水素原子を示し、ｎ
は整数である。〕[In the general formula (I), R 2 represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, and n
Is an integer. ]
【００１２】また、本発明はトリアルコキシシラン、ま
たはトリクロロシランの初期加水分解縮合物を原料とし
て、有機溶剤中、固形分濃度０．５〜３０重量％の濃度
でアルカリを触媒として、６０〜１４０℃に加熱して更
に縮合させて、上記ポリオルガノシルセスキオキサンを
製造する方法に関する。In the present invention, trialkoxysilane or an initial hydrolysis-condensation product of trichlorosilane is used as a raw material in an organic solvent at a solid content concentration of 0.5 to 30% by weight with an alkali as a catalyst and a concentration of 60 to 140. The present invention relates to a method of producing the above polyorganosilsesquioxane by heating at 0 ° C. and further condensing.
【００１３】以下、本発明を詳しく説明する。一般式
（Ｉ）で示される本発明のポリオルガノシルセスキオキ
サンにおいて、側鎖Ｒ1 は炭素１〜３のアルキル基、置
換または非置換フェニル基を示し、このうち５０モル％
以上、好ましくは８０モル％以上がメチル基であること
を必要とする。メチル基が５０モル％以下では本発明の
目的とする耐熱性、硬度が不満足となる。また側鎖Ｒ1
のメチル基以外の残りの基としては炭素原子数４以上の
アルキル基は耐熱性に悪影響を及ぼすため好ましくな
い。The present invention will be described in detail below. In the polyorganosilsesquioxane of the present invention represented by the general formula (I), the side chain R 1 represents an alkyl group having 1 to 3 carbon atoms or a substituted or unsubstituted phenyl group, of which 50 mol%
It is necessary that 80 mol% or more, preferably 80 mol% or more, be a methyl group. When the methyl group content is 50 mol% or less, the heat resistance and hardness aimed at by the present invention are unsatisfactory. The side chain R 1
As the remaining groups other than the methyl group, an alkyl group having 4 or more carbon atoms is not preferable because it adversely affects the heat resistance.
【００１４】本発明のポリオルガノシルセスキオキサン
において末端基を示すＲ2 は炭素原子数１ないし３個の
アルキル基または水素原子であり、これらは原料のトリ
アルコキシシランまたはトリクロロシランに由来するも
のである。炭素原子数は４個以上のトリアルコキシシラ
ンを原料とする場合では加水分解、縮合速度が遅く非実
用的である。末端基を例えばトリメチルクロロシラン、
トリメチルメトキシシランなどを用いてキャッピングし
て保存安定性を高めて使用することも可能である。In the polyorganosilsesquioxane of the present invention, R 2 which represents an end group is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, and these are derived from trialkoxysilane or trichlorosilane as a raw material. Is. When a trialkoxysilane having 4 or more carbon atoms is used as a raw material, the hydrolysis and condensation rates are slow and impractical. End groups such as trimethylchlorosilane,
It is also possible to enhance the storage stability by capping with trimethylmethoxysilane or the like before use.
【００１５】本発明のポリオルガノシルセスキオキサン
の数平均分子量はＧＰＣ装置と標準分子量物質を用いる
ことにより測定されるものであり、数平均分子量として
は１００，０００以上であることが必要である。数平均
分子量は１００，０００以下では溶液を基材に塗布後溶
剤が揮散した後も被膜がべたついたり、耐溶剤性や表面
硬度が不充分となるので好ましくない。The number average molecular weight of the polyorganosilsesquioxane of the present invention is measured by using a GPC device and a standard molecular weight substance, and it is necessary that the number average molecular weight is 100,000 or more. .. When the number average molecular weight is 100,000 or less, the coating becomes sticky and solvent resistance and surface hardness become insufficient even after the solution is applied to the substrate and the solvent is volatilized, which is not preferable.
【００１６】本発明のポリオルガノシルセスキオキサン
を製造するには、まず対応する原料のトリアルコキシシ
ランまたはトリクロロシランを加水分解縮合して初期縮
合物とする。この初期加水分解縮合での触媒は、酸また
はアルカリのいずれの触媒も使用可能であり、反応のコ
ントロールのしやすさからは酸触媒が好ましい。次いで
この初期縮合物を、有機溶剤中、固形分濃度０．５〜３
０重量％の濃度でアルカリを触媒として、６０〜１４０
℃に加熱して数平均分子量が１００，０００以上となる
よう、更に縮合を進める。In order to produce the polyorganosilsesquioxane of the present invention, first, the corresponding raw material trialkoxysilane or trichlorosilane is hydrolyzed and condensed to form an initial condensate. As the catalyst for this initial hydrolysis and condensation, either an acid catalyst or an alkali catalyst can be used, and an acid catalyst is preferred from the viewpoint of easy control of the reaction. Then, the initial condensate is treated with an organic solvent to obtain a solid content concentration of 0.5 to 3
60-140 with alkali as a catalyst at a concentration of 0% by weight
The condensation is further advanced by heating to 0 ° C. so that the number average molecular weight becomes 100,000 or more.
【００１７】本発明において縮合時の有機溶剤としては
メタノール、エタノール、イソプロパノール、ブタノー
ル等のアルコール類、テトラヒドロフラン、ジエチルエ
ーテル、ジエチレングリコールモノメチルエーテル、ジ
エチレングリコールモノブチルエーテルのようなエーテ
ル類、メチルエチルケトン、アセトン、メチルイソブチ
ルケトンのようなケトン類、酢酸エチル、酢酸メチル、
酢酸ブチルのようなエステル類、トルエン、キシレン、
ベンゼン、クロルベンゼンなどの芳香族炭化水素類、ジ
クロロエタン、トリクロロエタン、トリクロロエチレン
などのハロゲン化炭化水素類、その他ジメチルホルムア
ミド、ジメチルスルホキシド等の溶剤が例示される。In the present invention, as the organic solvent at the time of condensation, alcohols such as methanol, ethanol, isopropanol, butanol, etc., ethers such as tetrahydrofuran, diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, methyl ethyl ketone, acetone, methyl isobutyl ketone. Ketones such as ethyl acetate, methyl acetate,
Esters such as butyl acetate, toluene, xylene,
Examples thereof include aromatic hydrocarbons such as benzene and chlorobenzene, halogenated hydrocarbons such as dichloroethane, trichloroethane and trichloroethylene, and solvents such as dimethylformamide and dimethylsulfoxide.
【００１８】縮合時の触媒としては水酸化ナトリウム、
水酸化カリウム、水酸化リチウム、水酸化セシウムなど
アルカリ金属の水酸化物、トリエチルアミン、ジエチレ
ントリアミン、ｎ−ブチルアミン、Ｐ−ジメチルアミノ
エタノール、トリエタノールアミンなどのアミン類、テ
トラメチルアンモニウムハイドロキサイドのような四級
アンモニウム塩類を使用することができる。Sodium hydroxide is used as a catalyst for condensation.
Alkali metal hydroxides such as potassium hydroxide, lithium hydroxide, cesium hydroxide, amines such as triethylamine, diethylenetriamine, n-butylamine, P-dimethylaminoethanol, triethanolamine, and tetramethylammonium hydroxide. Quaternary ammonium salts can be used.
【００１９】本発明のポリオルガノシルセスキオキサン
の製造に際し、前述の有機溶剤に対して固形分濃度は３
０重量％以下とすることがよく、これ以上の固形分濃度
では縮合の進行と共にゲル化が生じやすくなる。またゲ
ル化が避けられても、生成物の保存安定性が乏しく保管
時にゲル化が起りやすい。一方０．５重量％以下の濃度
では縮合反応の速度が遅く、実用的ではない。In producing the polyorganosilsesquioxane of the present invention, the solid content concentration is 3 with respect to the above-mentioned organic solvent.
The content is preferably 0% by weight or less, and at a solid content concentration higher than this, gelation easily occurs as the condensation proceeds. Even if gelation is avoided, the product has poor storage stability, and gelation easily occurs during storage. On the other hand, at a concentration of 0.5% by weight or less, the condensation reaction rate is slow, which is not practical.
【００２０】縮合反応の温度は６０〜１４０℃が好まし
く、６０℃以下では反応を効率的に進めることができ
ず、１４０℃以上では逆にゲル化を抑制することが難し
い。縮合反応の停止は反応溶液を中和することにより行
い、その際に生じる塩は必要に応じて瀘過または水洗等
により除去する。また微量の水が問題となる場合は脱水
剤を用いて取り除くことができる。縮合反応のもう一つ
の副生物であるアルコールは加熱あるいは減圧蒸留によ
って容易に除去することが可能である。このようにして
本発明のポリオルガノシルセスキオキサンをゲル化する
ことなく安定に製造することができる。The temperature of the condensation reaction is preferably 60 to 140 ° C., the reaction cannot proceed efficiently at 60 ° C. or lower, and conversely it is difficult to suppress gelation at 140 ° C. or higher. The condensation reaction is stopped by neutralizing the reaction solution, and the salt generated at that time is removed by filtration or washing with water as necessary. If a trace amount of water is a problem, it can be removed by using a dehydrating agent. Another by-product of the condensation reaction, alcohol, can be easily removed by heating or vacuum distillation. In this way, the polyorganosilsesquioxane of the present invention can be stably produced without gelation.
【００２１】このポリオルガノシルセスキオキサンを使
用するに当っては、そのまま溶液として、濃縮、稀釈等
濃度や溶剤組成を修正して用いることもできるし、溶剤
を全て除いたフィルムや粉末状として取り出すこともで
きる。また本発明のポリオルガノシルセスキオキサンに
は必要に応じて各種の添加剤例えば充填剤、染料、顔
料、安定剤、紫外線吸収剤、防カビ剤、界面活性剤、レ
ベリンク剤などを添加して用いることもできる。In using this polyorganosilsesquioxane, it is possible to use it as a solution as it is, by concentrating, diluting, etc. and modifying the solvent composition, or by using it as a film or powder form without any solvent. You can also take it out. In addition, various additives such as fillers, dyes, pigments, stabilizers, ultraviolet absorbers, antifungal agents, surfactants, and leveling agents may be added to the polyorganosilsesquioxane of the present invention as necessary. It can also be used.
【００２２】本発明のポリオルガノシルセスキオキサン
はその溶液を基材表面に塗布し、溶剤を揮散させるだけ
で、強靱で、硬く、また５００℃の耐熱性を有する被膜
を形成させることができるが、この被膜を加熱硬化する
ことにより、更に硬度、耐溶剤性等の向上を図ることも
可能である。The polyorganosilsesquioxane of the present invention can form a tough, hard and heat-resistant coating at 500 ° C. only by coating the surface of the substrate with the solution and evaporating the solvent. However, it is possible to further improve hardness, solvent resistance and the like by heating and curing this coating.
【００２３】[0023]
【実施例】以下、実施例及び比較例をあげて本発明を更
に詳しく説明する。なお、実施例及び比較例中のポリオ
ルガノシルセスキオキサンの基本物性測定は下記の方法
により行った。EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. The basic physical properties of the polyorganosilsesquioxanes used in Examples and Comparative Examples were measured by the following methods.
【００２４】〔数平均分子量〕ＧＰＣ法による。装置は
島津製作所製ＣＲ−３Ａを使用しカラムは昭和電工
（株）製ショウデックスＫＦ８０１，ＫＦ８０２，ＫＦ
８０３，ＫＦ８０４を連結して使用し、標準試料ポリス
チレンとの比較換算により求めた。[Number average molecular weight] According to the GPC method. The equipment is Shimadzu CR-3A and the column is Showdex KF801, KF802, KF made by Showa Denko KK
803 and KF804 were connected and used, and it calculated | required by the comparison conversion with standard sample polystyrene.
【００２５】〔赤外線吸収スペクトル〕島津製作所製Ｉ
Ｒ−４３５を使用し、透過率測定により赤外吸収スペク
トルを調べた。[Infrared absorption spectrum] Shimadzu I
The infrared absorption spectrum was investigated by measuring the transmittance using R-435.
【００２６】〔Ｘ線回析〕理学電機（株）製ＲＩＧＡＫ
Ｕ ＲＯＤ−Ｂシステム（Ｘ線源はＣｕターゲット）を
使用した。[X-ray diffraction] RIGAK manufactured by Rigaku Denki Co., Ltd.
The U ROD-B system (the X-ray source is a Cu target) was used.
【００２７】（実施例１）１リットルの４つ口フラスコ
に、メチルトリエトキシシラン４８１．４ｇ（２．７モ
ル）、フェニルトリメトキシシラン５９．５ｇ（０．３
モル）、塩酸０．０００４モル、水１０８ｇ（６モル）
を仕込んだ後、フラスコ内の温度を５０℃まで昇温し、
撹拌しながら３０分間保持した。続いて７０℃に昇温
し、２時間反応させた後、エバポレーターを用いて水及
びアルコールを除いたところ、反応物約２６０ｇを得
た。次にこれをメチルイソブチルケトンに固形分濃度が
１５重量％になるよう溶解しトリエチルアミン０．００
８２モルを滴下し、８０℃で３時間反応せしめた後、塩
酸０．００８７モルを加えて中和した。(Example 1) 481.4 g (2.7 mol) of methyltriethoxysilane and 59.5 g (0.3 mol) of phenyltrimethoxysilane were placed in a 1-liter four-necked flask.
Mol), hydrochloric acid 0.0004 mol, water 108 g (6 mol)
After charging, the temperature in the flask was raised to 50 ° C.,
Hold for 30 minutes with stirring. Subsequently, the temperature was raised to 70 ° C., the reaction was carried out for 2 hours, and then water and alcohol were removed using an evaporator to obtain about 260 g of a reaction product. Next, this was dissolved in methyl isobutyl ketone so that the solid content concentration was 15% by weight, and triethylamine was added to 0.003%.
After adding 82 mol dropwise and reacting at 80 ° C. for 3 hours, 0.0087 mol of hydrochloric acid was added to neutralize.
【００２８】この反応物の分子量をＧＰＣにより求めた
ところ、数平均分子量は３５０，０００であった。ＧＰ
Ｃ溶出曲線から見られるこの反応物の分子量分布は一般
のシリコーン系化合物に比して狭かった。またこの溶液
をシリコンウェハー上にスピンコートし、溶剤を完全に
除去した後のフィルムの赤外吸収スペクトルではＳｉ−
Ｏ−Ｓｉの伸縮振動が１０３０ｃｍ-1と１１００ｃｍ-1
とに大きく分岐し、ポリシルセスキオキサンの構造が確
認された。なお、このスペクトルの帰属については第３
回無機高分子講演要旨集第３５頁の記載を引用、準拠し
た。When the molecular weight of this reaction product was determined by GPC, the number average molecular weight was 350,000. GP
The molecular weight distribution of this reaction product as seen from the C elution curve was narrower than that of general silicone compounds. The solution was spin-coated on a silicon wafer and the solvent was completely removed.
Stretching vibration of O-Si is 1030 cm -1 and 1100 cm -1
The structure of polysilsesquioxane was confirmed by branching to and. For the attribution of this spectrum, see
The description on page 35 of the Abstracts of Inorganic Polymer Lectures was cited and conformed.
【００２９】また上記フィルムのＸ線回析図は、４．５
Åに明瞭な回析ピークを有しており、Brownらがポリシ
ルセスキオキサンに対して測定した値に一致した。The X-ray diffraction pattern of the above film is 4.5.
It has a clear diffraction peak at Å, which agrees with the value measured by Brown et al. For polysilsesquioxane.
【００３０】上記フィルムは、鉛筆硬度Ｈの比較的硬い
被膜であり、うすい金属板にコーティングした被膜では
１８０度折り曲げにも追従しうる柔軟性を示した。ま
た、これを５００℃で１時間熱処理を行ったが何ら損傷
は見られず、鉛筆硬度は６Ｈに向上した。The above film was a relatively hard coating having a pencil hardness of H, and a coating coated on a thin metal plate showed flexibility capable of following 180-degree bending. Moreover, this was heat-treated at 500 ° C. for 1 hour, but no damage was observed, and the pencil hardness was improved to 6H.
【００３１】（比較例１）実施例１において、縮合時の
固形分濃度を０．２重量％とする以外は実施例１と同様
な操作、処方によりポリオルガノシルセスキオキサンを
合成した。８０℃３時間後の反応物のＧＰＣによる数平
均分子量は５０，０００であった。この溶液を固形分濃
度１５％となるよう濃縮し、実施例１と同様にシリコン
ウェハー上にスピンコートし、溶剤を完全に除去した
が、フィルムはベタつき、硬度は全く得られなかった。(Comparative Example 1) Polyorganosilsesquioxane was synthesized by the same operation and formulation as in Example 1 except that the solid content concentration at the time of condensation was 0.2% by weight. The number average molecular weight by GPC of the reaction product after 3 hours at 80 ° C. was 50,000. This solution was concentrated to a solid content concentration of 15% and spin-coated on a silicon wafer in the same manner as in Example 1 to completely remove the solvent, but the film was sticky and no hardness was obtained at all.
【００３２】（比較例２）実施例１において、縮合時の
固形分濃度を３５重量％とする以外は実施例１と同様な
操作、処方によりポリオルガノシルセスキオキサンを合
成した。８０℃３時間後の反応物の数平均分子量は６５
０，０００であった後、常温で保存一昼夜後この溶液は
ゲル化を生じた。Comparative Example 2 A polyorganosilsesquioxane was synthesized by the same operation and formulation as in Example 1 except that the solid content concentration during condensation was 35% by weight. The number average molecular weight of the reaction product after 3 hours at 80 ° C. is 65.
After being stored at room temperature, the solution gelled.
【００３３】（比較例３）実施例１において、縮合時の
反応温度を５０℃とする以外は実施例１と同様な操作、
処方によりポリオルガノシルセスキオキサンを合成し
た。３時間後の反応物の数平均分子量は６２，０００で
あり、本発明の目的とする分子量域には達していなかっ
た。Comparative Example 3 The same operation as in Example 1 except that the reaction temperature at the time of condensation is 50 ° C.
Polyorganosilsesquioxane was synthesized by the formulation. The number average molecular weight of the reaction product after 3 hours was 62,000, which did not reach the target molecular weight range of the present invention.
【００３４】（比較例４）実施例１において、縮合時の
溶剤をシクロヘキサノール、縮合時の反応温度を１４５
℃とする以外は実施例１と同様な操作、処方によりポリ
オルガノシルセスキオキサンを合成した。反応２時間後
にゲル化し、沈澱を生じた。(Comparative Example 4) In Example 1, the solvent at the time of condensation was cyclohexanol, and the reaction temperature at the time of condensation was 145.
Polyorganosilsesquioxane was synthesized by the same operation and formulation as in Example 1 except that the temperature was changed to ° C. After 2 hours of reaction, gelation occurred and precipitation occurred.
【００３５】（実施例２）１リットルの４つ口フラスコ
に、メチルトリエトキシシラン３２０．９ｇ（１．８モ
ル）、プロピルトリエトキシシラン２４７．６ｇ（１．
２モル）、塩酸０．０００４モル、水１０８ｇ（６モ
ル）を仕込んだ後、フラスコ内の温度を５０℃まで昇温
し、撹拌しながら３０分間保持した。続いて７０℃に昇
温し、２時間反応させた後、エバポレーターを用いて水
及びアルコールを除いたところ、反応物約２７０ｇを得
た。次にこれを酢酸ブチルに固形分濃度が５重量％にな
るよう溶解し、エタノールアミン０．００８２モルを滴
下し、７０℃で５時間反応せしめた後、酢酸０．００８
７モルを加えて中和した。この反応物の分子量をＧＰＣ
により求めたところ、数平均分子量は１，１５０，００
０であった。実施例１と同様にこれをシリコンウェハー
上にスピンコートし、溶剤を完全に除去したところ、鉛
筆硬度Ｆの比較的硬い被膜が得られた。さらにこの被膜
に３００℃で１時間熱処理を行ったが、何ら異常は見ら
れず鉛筆硬度は２Ｈに向上した。(Example 2) In a 1-liter four-necked flask, 320.9 g (1.8 mol) of methyltriethoxysilane and 247.6 g (1.
(2 mol), 0.0004 mol of hydrochloric acid, and 108 g (6 mol) of water were charged, and then the temperature in the flask was raised to 50 ° C. and kept for 30 minutes while stirring. Subsequently, the temperature was raised to 70 ° C., the reaction was carried out for 2 hours, and then water and alcohol were removed using an evaporator to obtain about 270 g of a reaction product. Next, this was dissolved in butyl acetate so that the solid content concentration was 5% by weight, 0.0082 mol of ethanolamine was added dropwise, and the mixture was reacted at 70 ° C. for 5 hours, and then 0.008% of acetic acid was added.
7 mol was added to neutralize. The molecular weight of this reaction product is determined by GPC
The number average molecular weight was 1,150,00.
It was 0. When a silicon wafer was spin-coated and the solvent was completely removed in the same manner as in Example 1, a relatively hard coating having a pencil hardness F was obtained. Further, this coating was heat-treated at 300 ° C. for 1 hour, but no abnormality was found and the pencil hardness was improved to 2H.
【００３６】（比較例５）実施例２におけるメチルトリ
エトキシシランを１．２モル、プロピルトリエトキシシ
ラン１．８モルとする以外は実施例１と同様な操作、処
方によりポリオルガノシルセスキオキサンを合成した。
反応３時間後の数平均分子量は９８０，０００であっ
た。シリコンウェハー上に作製した被膜は鉛筆硬度２Ｂ
と軟らかく、また３００℃で１時間加熱処理を行ったと
ころ多数のクラックを生じた。(Comparative Example 5) A polyorganosilsesquioxane was prepared in the same manner as in Example 1 except that 1.2 mol of methyltriethoxysilane and 1.8 mol of propyltriethoxysilane were used in Example 2. Was synthesized.
The number average molecular weight after 3 hours of reaction was 980,000. The film produced on a silicon wafer has a pencil hardness of 2B.
It was soft, and when heat-treated at 300 ° C. for 1 hour, many cracks were generated.
【００３７】[0037]
【発明の効果】以上説明したように、本発明のポリオル
ガノシルセスキオキサンは、その溶液を基材にコーティ
ングし溶剤を揮発させるだけで、強靱で硬度が高く、ま
た５００℃に耐える耐熱性の被膜を形成することができ
る。このため、プロセス的にも簡便となる他、従来加熱
硬化に適しない基材にも適用することができ、広い用途
に使用することが可能である。As described above, the polyorganosilsesquioxane of the present invention is tough, has high hardness, and is heat resistant to withstand 500 ° C. only by coating the solution with the substrate and evaporating the solvent. Can be formed. Therefore, the process is simple, and it can be applied to a base material which is not suitable for conventional heat curing, and can be used for a wide range of purposes.
Claims (2)
ガノシルセスキオキサンにおいて、全側鎖Ｒ1 の５０〜
１００モル％がメチル基であり、残部が炭素原子数２な
いし３個のアルキル基か置換または非置換フェニル基で
あり、Ｒ2 が炭素原子数１ないし３個のアルキル基また
は水素原子であり、ｎが整数であり、数平均分子量が１
００，０００以上であることを特徴とするポリオルガノ
シルセスキオキサン。 【化１】 1. In the polyorganosilsesquioxane represented by the general formula (I), 50 to 50% of all side chains R 1 are used.
100 mol% is a methyl group, the remainder is an alkyl group having 2 to 3 carbon atoms or a substituted or unsubstituted phenyl group, and R 2 is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, n is an integer and the number average molecular weight is 1
A polyorganosilsesquioxane having a content of at least 0,000. [Chemical 1]
ロシランの初期加水分解縮合物を原料として、有機溶剤
中、固形分濃度０．５〜３０重量％の濃度でアルカリを
触媒として、６０〜１４０℃に加熱して更に縮合するこ
とを特徴とする請求項第１項記載のポリオルガノシルセ
スキオキサンの製造方法。2. A trialkoxysilane or an initial hydrolysis-condensation product of trichlorosilane is used as a raw material and heated to 60 to 140 ° C. in an organic solvent at a solid content concentration of 0.5 to 30% by weight with an alkali as a catalyst. The method for producing a polyorganosilsesquioxane according to claim 1, wherein the polyorganosilsesquioxane is further condensed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22189891A JP3272002B2 (en) | 1991-09-02 | 1991-09-02 | Method for producing polyorganosilsesquioxane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22189891A JP3272002B2 (en) | 1991-09-02 | 1991-09-02 | Method for producing polyorganosilsesquioxane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05125187A true JPH05125187A (en) | 1993-05-21 |
| JP3272002B2 JP3272002B2 (en) | 2002-04-08 |
Family
ID=16773897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22189891A Expired - Fee Related JP3272002B2 (en) | 1991-09-02 | 1991-09-02 | Method for producing polyorganosilsesquioxane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3272002B2 (en) |
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| US5939500A (en) * | 1997-02-24 | 1999-08-17 | Dow Corning Asia, Ltd | Hydrogen-functional silylated polymethylsilsesquioxane |
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