JP2001040094A - Epoxy group-containing silicone resin - Google Patents
Epoxy group-containing silicone resinInfo
- Publication number
- JP2001040094A JP2001040094A JP11217408A JP21740899A JP2001040094A JP 2001040094 A JP2001040094 A JP 2001040094A JP 11217408 A JP11217408 A JP 11217408A JP 21740899 A JP21740899 A JP 21740899A JP 2001040094 A JP2001040094 A JP 2001040094A
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- JP
- Japan
- Prior art keywords
- group
- epoxy group
- silicone resin
- methyl
- condensation polymerization
- 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.)
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- Silicon Polymers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はシリコーン樹脂にお
ける耐クラック性及び接着性の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in crack resistance and adhesiveness of a silicone resin.
【０００２】[0002]
【従来の技術】シリコーン樹脂は、耐熱性、電気特性、
光学特性、耐候性等に優れているため、これらの性能を
必要とする分野に広く利用されているが、その硬化物は
脆くてクラックが入りやすく、また接着性にも問題があ
るため、用途が限られている。2. Description of the Related Art Silicone resin has heat resistance, electrical properties,
Because of its excellent optical properties and weather resistance, it is widely used in fields that require these properties.However, the cured product is brittle and easily cracks, and there is also a problem with adhesiveness. Is limited.
【０００３】[0003]
【発明が解決しようとする課題】従って本発明の目的
は、シリコーン樹脂本来の耐熱性、電気特性、光学特
性、耐候性等の特性を維持しながら、耐クラック性及び
接着性に優れた硬化物を与えるエポキシ基含有シリコー
ン樹脂を提供することである。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a cured product having excellent crack resistance and adhesion while maintaining the inherent heat resistance, electrical properties, optical properties, weather resistance, etc. of a silicone resin. Is to provide an epoxy group-containing silicone resin.
【０００４】[0004]
【課題を解決するための手段】本発明者は、従来技術に
おける上記欠点を克服するため、種々検討を行った結
果、非常に高分子の状態でエポキシ基を導入でき、これ
により得られるエポキシ基含有シリコーン樹脂は耐クラ
ック性及び接着性に優れた硬化物を形成できることを見
い出し、本発明に到達した。即ち本発明は、平均組成式
（１）： （ＨＯ）aＲ1ＳｉＯ(3-a)/2 （１） （但し、Ｒ1はメチル基、エチル基、プロピル基、ビニ
ル基又はフェニル基を表し、ａは0.02〜2の正数であ
る。）で示される、分子量130〜5,000のシラノール基含
有オルガノポリシロキサンと、下記一般式（２）：The inventor of the present invention has conducted various studies to overcome the above-mentioned disadvantages of the prior art, and as a result, has been able to introduce an epoxy group in a very high polymer state. The present inventors have found that a silicone resin can form a cured product having excellent crack resistance and adhesion, and have reached the present invention. That is, the present invention provides an average composition formula (1): (HO) a R 1 SiO (3-a) / 2 (1) (where R 1 represents a methyl group, an ethyl group, a propyl group, a vinyl group or a phenyl group) Wherein a is a positive number of 0.02 to 2), and a silanol group-containing organopolysiloxane having a molecular weight of 130 to 5,000, and the following general formula (2):
【０００５】[0005]
【化２】 で示されるエポキシ基含有ジシロキサン化合物とを縮合
重合させることにより得られたエポキシ基含有シリコー
ン樹脂を提供する。Embedded image The present invention provides an epoxy group-containing silicone resin obtained by subjecting an epoxy group-containing disiloxane compound represented by the following to condensation polymerization.
【０００６】[0006]
【発明の実施の形態】以下、本発明を詳細に説明する。 製造原料：本発明のエポキシ基含有シリコーン樹脂の原
料として使用されるシラノール基（即ち、ケイ素原子に
結合したヒドロキシル基）含有オルガノポリシロキサン
は、平均組成式（１）： （ＨＯ）aＲ1ＳｉＯ(3-a)/2 （１） で示されるものである。ここで、Ｒ1はメチル基、エチ
ル基、プロピル基、ビニル基又はフェニル基を表し、好
ましくはメチル基又はフェニル基を表し、ａは0.02〜
2、好ましくは0.05〜1、より好ましくは0.1〜0.8の正数
である。このシラノール基含有オルガノポリシロキサン
の分子量は、ゲルパーミエーションクロマトグラフィー
（ＧＰＣ）によるポリスチレン換算の重量平均分子量
で、130〜5,000、好ましくは170〜4,000、より好ましく
は200〜2,500程度である。この分子量が130未満では、
後述する一般式（２）で示されるエポキシ基含有ジシロ
キサン化合物との縮合重合生成物から得られる硬化被膜
が耐クラック性に劣ったものとなり、また5,000を超え
ると、上記エポキシ基含有ジシロキサン化合物との反応
中において、ゲル化が起こりやすく、目的の縮合重合生
成物を得るのが困難である。このシラノール基含有オル
ガノポリシロキサンは基本的に分岐状及び／又は三次元
網状構造のものであり、例えば次のような公知の製造方
法で容易に得ることができる。即ち、有機溶媒（例えば
トルエン、ジイソプロピルエーテル等の極性又は非極性
有機溶媒）と水との混合溶媒中、攪拌下に一般式
（３）： Ｒ1ＳｉＸ3 （３） （但し、Ｘは水酸基、塩素原子、メトキシ基、エトキシ
基、プロポキシ基、ブトキシ基、メトキシエトキシ基等
のアルコキシ基などの、加水分解性基であり、Ｒ 1は前
述したとおりである。）で示される、１分子中に３個の
加水分解性基を有する、いわゆる３官能性シラン化合物
の有機溶媒溶液（有機溶媒は前記と同様）を滴下し、次
いでこれを加熱重合、水洗、ストリップの順次工程で処
理して得られる。なお、Ｘが塩素原子以外の加水分解性
基である場合には、有機溶媒と水との混合溶媒中に加水
分解触媒を併用することが好ましい。この場合、水の
量、重合温度等の条件により平均組成式（１）で示され
るシラノール基含有オルガノポリシロキサン生成物中の
0H量及び分子量を調整することができる。本発明のエポ
キシ基含有シリコーン樹脂の原料として使用されるエポ
キシ基含有ジシロキサン化合物は、下記一般式（２）：BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Production raw material: raw material for the epoxy group-containing silicone resin of the present invention
Silanol group used as a raw material (that is,
Bonded hydroxyl group-containing organopolysiloxane
Is the average composition formula (1): (HO)aR1SiO(3-a) / 2 (1) Where R1Is a methyl group,
A phenyl group, a propyl group, a vinyl group or a phenyl group.
Preferably represents a methyl group or a phenyl group, a is 0.02 ~
2, preferably a positive number between 0.05 and 1, more preferably between 0.1 and 0.8
It is. This silanol group-containing organopolysiloxane
Molecular weight is determined by gel permeation chromatography
Weight average molecular weight in terms of polystyrene by (GPC)
At 130-5,000, preferably 170-4,000, more preferably
Is around 200-2,500. If this molecular weight is less than 130,
An epoxy group-containing disilicone represented by the following general formula (2)
Cured coating obtained from condensation polymerization product with xanthate compound
Has poor crack resistance, and exceeds 5,000
Reacts with the epoxy group-containing disiloxane compound
Gelation is likely to occur in
It is difficult to obtain a product. This silanol group-containing
Ganopolysiloxanes are basically branched and / or three-dimensional
It has a net-like structure, for example, the following known manufacturing method
It can be easily obtained by the method. That is, an organic solvent (for example,
Polar or non-polar such as toluene and diisopropyl ether
Organic solvent) and water in a mixed solvent of general formula
(3): R1SixThree (3) (where X is a hydroxyl group, chlorine atom, methoxy group, ethoxy
Group, propoxy group, butoxy group, methoxyethoxy group, etc.
A hydrolyzable group such as an alkoxy group of 1Is before
As described above. ), Three molecules in one molecule
A so-called trifunctional silane compound having a hydrolyzable group
Of an organic solvent (the organic solvent is the same as described above)
Then, heat treatment, water washing and stripping are performed in this order.
It is obtained by processing. Note that X is a hydrolyzable compound other than a chlorine atom.
If it is a group, it is added to a mixed solvent of an organic solvent and water.
It is preferable to use a decomposition catalyst in combination. In this case, the water
It is represented by the average composition formula (1) depending on conditions such as the amount and polymerization temperature.
In silanol group-containing organopolysiloxane products
The 0H amount and molecular weight can be adjusted. Epo of the present invention
Epoxy used as a raw material for xy group-containing silicone resin
The xy group-containing disiloxane compound has the following general formula (2):
【０００７】[0007]
【化３】 で示されるもので、公知の化合物であり、例えば特開平
４−１２４１９３号に記載の製造方法で容易に得ること
ができる。Embedded image Which is a known compound and can be easily obtained, for example, by the production method described in JP-A-4-124193.
【０００８】製造方法：本発明のエポキシ基含有シリコ
ーン樹脂は、平均組成式（１）のシラノール基含有オル
ガノポリシロキサンと一般式（２）のエポキシ基含有ジ
シロキサン化合物とを、縮合重合させることにより製造
される。詳しくは、上記２つの成分を、オルガノポリシ
ロキサン中のOH基／ジシロキサン化合物中のメトキシ基
などのＯＲ3基が１／１〜１／２（モル比）となるよう
に混合し、これを有機溶媒中、縮合触媒の存在下に加熱
して、縮重合反応させることにより製造される。Production method: The epoxy group-containing silicone resin of the present invention is obtained by subjecting the silanol group-containing organopolysiloxane of the average compositional formula (1) to an epoxy group-containing disiloxane compound of the general formula (2) by condensation polymerization. Manufactured. Specifically, the two components are mixed as OR 3 groups such as OH groups / disiloxane methoxy group in the compound of the organopolysiloxane is 1 / 1-1 / 2 (molar ratio), this It is produced by heating in an organic solvent in the presence of a condensation catalyst to cause a condensation polymerization reaction.
【０００９】ここで使用可能な有機溶媒としては例え
ば、トルエン、キシレン等の芳香族系溶媒；アセトン、
メチルエチルケトン、メチルイソブチルケトン、シクロ
ヘキサノン等のケトン系溶媒；ジエチルエーテル、メチ
ルイソブチルエーテル、ジイソプロピルエーテル、ジブ
チルエーテル、テトラヒドロフラン、ジオキサン等のエ
ーテル系溶媒等が挙げられる。縮合触媒としては、例え
ばオルトチタン酸イソプロピルエステル、酸化アルミニ
ウム、ジブチルスズジオクテート等が挙げられる。加熱
温度は50〜150℃の範囲が適当で、この温度範囲で反応
は有効に進行する。低すぎると反応の進行が遅いし、ま
た高すぎるとエポキシ基の開環の原因となる。Examples of the organic solvent usable here include aromatic solvents such as toluene and xylene; acetone,
Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ether solvents such as diethyl ether, methyl isobutyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran and dioxane; Examples of the condensation catalyst include isopropyl orthotitanate, aluminum oxide, dibutyltin dioctate and the like. The heating temperature is suitably in the range of 50 to 150 ° C., and the reaction proceeds effectively in this temperature range. If it is too low, the progress of the reaction will be slow, and if it is too high, it will cause ring opening of the epoxy group.
【００１０】こうしてシラノール基含有オルガノポリシ
ロキサンとエポキシ基含有ジシロキサン化合物とを充分
反応させると同時に、上記反応温度で熟成させた後、溶
媒を留去し、続いて減圧下にストリッピングする。得ら
れた固体を少量の溶媒に溶解して溶液とし、該溶液を濾
過した後、貧溶媒中に注ぎ再沈させる。得られた沈澱を
濾過、乾燥することにより、エポキシ基含有シリコーン
樹脂は白色粉末として得られる。ここで使用可能な溶媒
としては、例えばトルエン、キシレン等の芳香族系溶
媒；アセトン、メチルエチルケトン、メチルイソブチル
ケトン、シクロヘキサノン等のケトン系溶媒；ジエチル
エーテル、メチルイソブチルエーテル、ジイソプロピル
エーテル、ジブチルエーテル、テトラヒドロフラン、ジ
オキサン等のエーテル系溶媒等が挙げられる。貧溶媒と
しては、ペンタン、ヘキサン、シクロヘキサン等の脂肪
族炭化水素系溶媒が適している。以上のようにして得ら
れる本発明のエポキシ基含有シリコーン樹脂は、通常、
８０〜２５０℃程度での加熱硬化により、耐クラック性
及び接着性に優れた硬化物を形成することができる。In this manner, the silanol group-containing organopolysiloxane and the epoxy group-containing disiloxane compound are sufficiently reacted and, at the same time, aged at the above reaction temperature, the solvent is distilled off, and then stripping is performed under reduced pressure. The obtained solid is dissolved in a small amount of a solvent to form a solution. The solution is filtered, poured into a poor solvent, and reprecipitated. By filtering and drying the obtained precipitate, the epoxy group-containing silicone resin is obtained as a white powder. Examples of the solvent usable herein include aromatic solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; diethyl ether, methyl isobutyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, Examples include ether solvents such as dioxane. As the poor solvent, aliphatic hydrocarbon solvents such as pentane, hexane, and cyclohexane are suitable. The epoxy group-containing silicone resin of the present invention obtained as described above is usually
By heating and curing at about 80 to 250 ° C., a cured product having excellent crack resistance and adhesiveness can be formed.
【００１１】用途：本発明のエポキシ基含有シリコーン
樹脂は、半導体素子用コーティング剤、半導体素子用接
着剤、素子製造プロセスでの層間絶縁膜、オプティカル
ファイバー用コーティング剤、オプティカルファイバー
用クラッド剤、プラスチックファイバーコア剤、光ガイ
ドコア剤、光導波路コア剤、光導波路クラッド剤、プラ
イマー、フィラー表面処理剤、有機樹脂改質剤、難燃化
剤、塗料添加剤、ハードコート剤、防湿含浸剤、半田レ
ジスト、フォトレジスト等として利用できる。Applications: The epoxy group-containing silicone resin of the present invention is used as a coating agent for semiconductor elements, an adhesive for semiconductor elements, an interlayer insulating film in an element manufacturing process, a coating agent for optical fibers, a cladding agent for optical fibers, and a plastic fiber. Core agent, optical guide core agent, optical waveguide core agent, optical waveguide clad agent, primer, filler surface treatment agent, organic resin modifier, flame retardant, paint additive, hard coat agent, moisture proof impregnating agent, solder resist , And photoresist.
【００１２】[0012]
【実施例】以下に本発明を実施例によって説明する。例
中、Ｍｅはメチル基を表し、またＧＰＣによる分子量と
は、ＧＰＣによるポリスチレン換算の重量平均分子量を
意味する。The present invention will be described below with reference to examples. In the examples, Me represents a methyl group, and the molecular weight by GPC means a weight average molecular weight in terms of polystyrene by GPC.
【００１３】 実施例１ 平均組成式（１）においてＲ1がフェニル基、ａが0.67である、ＧＰＣによる 分子量が1,000のシラノール基含有オルガノポリシロキサン（OH基含有量：0.5モ ル/100g） 100ｇ（OH基含有量：0.5モル） 一般式（２）においてＲ2がExample 1 In a mean composition formula (1), R 1 is a phenyl group, and a is 0.67. Silanol group-containing organopolysiloxane having a molecular weight of 1,000 by GPC (OH group content: 0.5 mol / 100 g) 100 g (OH group content: 0.5 mol) In the general formula (2), R 2 is
【００１４】[0014]
【化４】 Embedded image
【００１５】 で示されるγ−グリシドキシプロピル基であり、Ｒ3がメチル基である、エポキ シ基含有ジシロキサン化合物（分子量：426） 53.3ｇ（0.125モル）（メトキシ基含有量：0.5モル） オルトチタン酸イソプロピルエステル 0.1ｇ トルエン 300ｍｌ よりなる混合物を窒素雰囲気中、100℃で12時間加熱し
て反応、熟成した後、トルエンを常圧で留去し、更に真
空下150℃で1時間ストリップを行い、固体を得た。これ
を少量のトルエンに溶解し、大量のヘキサン中で再沈、
乾燥し、白色固体状の樹脂を100g(収率：72.8％)得た。
得られたエポキシ基含有シリコーン樹脂においては、IR
スペクトルの測定結果から、シラノール基含有オルガノ
ポリシロキサンに由来するOH基が消失し、またエポキシ
基含有ジシロキサン化合物の付加を示す−CH2−の吸収
が認められ、エポキシ基含有ジシロキサン化合物に由来
するメトキシ基が完全に消失していた。該樹脂のＧＰＣ
による分子量は、15,000であり、またエポキシ基の含有
量はO.18モル/100gであった。次に、該樹脂をトルエン
に溶解して溶液とし、これをガラス基板上に塗布し、10
0℃で30分間乾燥した後、得られた塗膜を150℃/1時間＋
250℃/2時間の条件で硬化させ、膜厚20μmの硬化膜を形
成した。この硬化膜には、クラックの発生は見られず、
またガラス基板によく接着していた。またこの硬化膜は
トルエン、テトラヒドロフラン、ジイソプロピルエーテ
ル、ジグライム及びメチルイソブチルケトンに不溶であ
った。53.3 g (0.125 mol) of an epoxy group-containing disiloxane compound (molecular weight: 426) which is a γ-glycidoxypropyl group represented by and R 3 is a methyl group (methoxy group content: 0.5 mol) A mixture of 0.1 g of isopropyl orthotitanate and 300 ml of toluene was heated at 100 ° C for 12 hours in a nitrogen atmosphere to react and ripen. Then, toluene was distilled off at normal pressure and stripped at 150 ° C for 1 hour under vacuum. Was performed to obtain a solid. This was dissolved in a small amount of toluene and reprecipitated in a large amount of hexane.
After drying, 100 g (yield: 72.8%) of a resin as a white solid was obtained.
In the obtained epoxy group-containing silicone resin, IR
From the spectrum measurement results, the OH group derived from the silanol group-containing organopolysiloxane disappeared, and the absorption of -CH 2- indicating the addition of the epoxy group-containing disiloxane compound was observed, which was attributed to the epoxy group-containing disiloxane compound. The methoxy group disappeared completely. GPC of the resin
And the content of epoxy group was 0.18 mol / 100 g. Next, the resin was dissolved in toluene to form a solution, which was applied on a glass substrate,
After drying at 0 ° C for 30 minutes, the obtained coating film was heated at 150 ° C for 1 hour +
The composition was cured at 250 ° C. for 2 hours to form a cured film having a thickness of 20 μm. No cracks are seen in this cured film,
It was well adhered to the glass substrate. This cured film was insoluble in toluene, tetrahydrofuran, diisopropyl ether, diglyme and methyl isobutyl ketone.
【００１６】 実施例２ 平均組成式（１）においてＲ1がフェニル基、ａが0.67である、ＧＰＣによる 分子量が1,000のシラノール基含有オルガノポリシロキサン（OH基含有量：0.5モ ル/100g） 100ｇ（OH基含有量：0.5モル） 一般式（２）においてＲ2がExample 2 Silanol group-containing organopolysiloxane having a molecular weight of 1,000 according to GPC and having an average composition formula (1) wherein R 1 is a phenyl group and a is 0.67 (OH group content: 0.5 mol / 100 g) 100 g (OH group content: 0.5 mol) In the general formula (2), R 2 is
【００１７】[0017]
【化５】 Embedded image
【００１８】 で示されるβ−３，４−エポキシシクロヘキシルエチル基であり、Ｒ3がメチル 基である、エポキシ基含有ジシロキサン化合物（分子量：446） 55.8ｇ（0.125モル）（メトキシ基含有量：0.5モル） オルトチタン酸イソプロピルエステル 0.1ｇ トルエン 300ｍｌ よりなる混合物を窒素雰囲気中、100℃で12時間加熱し
て反応、熟成した後、トルエンを常圧で留去し、更に真
空下150℃で1時間ストリップを行い、固体を得た。これ
を少量のトルエンに溶解し、大量のヘキサン中で再沈、
乾燥し、白色固体状の樹脂を125g(収率：89.3％)得た。
得られたエポキシ基含有シリコーン樹脂においては、IR
スペクトルの測定結果から、シラノール基含有オルガノ
ポリシロキサンに由来するOH基が消失し、またエポキシ
基含有ジシロキサン化合物の付加を示す−CH2−の吸収
が認められ、エポキシ基含有ジシロキサン化合物に由来
するメトキシ基が完全に消失していた。該樹脂のＧＰＣ
による分子量は、10,000であり、またエポキシ基の含有
量はO.17モル/100gであった。次に、該樹脂をトルエン
に溶解して溶液とし、これをガラス基板上に塗布し、10
0℃で30分間乾燥した後、150℃/1時間＋250℃/2時間の
条件で硬化させ、膜厚20μmの硬化膜を形成した。この
硬化膜には、クラックの発生は見られず、またガラス基
板によく接着していた。またこの硬化膜はトルエン、テ
トラヒドロフラン、ジイソプロピルエーテル、ジグライ
ム及びメチルイソブチルケトンに不溶であった。55.8 g (0.125 mol) of an epoxy group-containing disiloxane compound (molecular weight: 446) wherein β is a β-3,4-epoxycyclohexylethyl group and R 3 is a methyl group 0.5 mol) Isopropyl orthotitanate 0.1 g Toluene 300 ml A mixture consisting of 300 ml was heated at 100 ° C. for 12 hours in a nitrogen atmosphere to react and ripen. Stripping was performed for an hour to obtain a solid. This was dissolved in a small amount of toluene and reprecipitated in a large amount of hexane.
After drying, 125 g (yield: 89.3%) of a white solid resin was obtained.
In the obtained epoxy group-containing silicone resin, IR
From the spectrum measurement results, the OH group derived from the silanol group-containing organopolysiloxane disappeared, and the absorption of -CH 2- indicating the addition of the epoxy group-containing disiloxane compound was observed, which was attributed to the epoxy group-containing disiloxane compound. The methoxy group disappeared completely. GPC of the resin
And the content of epoxy group was 0.17 mol / 100 g. Next, the resin was dissolved in toluene to form a solution, which was applied on a glass substrate,
After drying at 0 ° C. for 30 minutes, it was cured at 150 ° C./1 hour + 250 ° C./2 hours to form a cured film having a thickness of 20 μm. No cracks were observed in the cured film, and the cured film was well adhered to the glass substrate. The cured film was insoluble in toluene, tetrahydrofuran, diisopropyl ether, diglyme and methyl isobutyl ketone.
【００１９】 実施例３ 平均組成式（１）においてＲ1がフェニル基又はメチル基（フェニル基／メチ ル基＝50モル／50モル）、ａが0.25である、ＧＰＣによる分子量が1,500のシラ ノール基含有オルガノポリシロキサン（OH基含有量：0.25モル/100g） 100ｇ（OH基含有量：0.25モル） 一般式（２）においてＲ2がExample 3 In the average compositional formula (1), R 1 is a phenyl group or a methyl group (phenyl group / methyl group = 50 mol / 50 mol), a is 0.25, and a GPC-based silanol having a molecular weight of 1,500. Group-containing organopolysiloxane (OH group content: 0.25 mol / 100 g) 100 g (OH group content: 0.25 mol) In the general formula (2), R 2 is
【００２０】[0020]
【化６】 Embedded image
【００２１】 で示されるγ−グリシドキシプロピル基であり、Ｒ3がメチル基である、エポキ シ基含有ジシロキサン化合物（分子量：426） 29.8ｇ（0.07モル）（メトキシ基含有量：0.28モル） オルトチタン酸イソプロピルエステル 0.1ｇ トルエン 300ｍｌ よりなる混合物を窒素雰囲気中、100℃で12時間加熱し
て反応、熟成した後、トルエンを常圧で留去し、更に真
空下150℃で1時間ストリップを行い、固体を得た。これ
を少量のトルエンに溶解し、大量のヘキサン中で再沈、
乾燥し、白色固体状の樹脂を105g(収率：86.6％)得た。
こうして得られたエポキシ基含有シリコーン樹脂におい
ては、IRスペクトルの測定結果から、シラノール基含有
オルガノポリシロキサンのOH基が消失し、またエポキシ
基含有ジシロキサン化合物の付加を示す−CH2−の吸収
が認められた。該樹脂のＧＰＣによる分子量は、17,000
であり、またエポキシ基の含有量はO.11モル/100gであ
った。次に、該樹脂をトルエンに溶解して溶液とし、こ
れをガラス基板上に塗布し、100℃で30分間乾燥し、得
られた塗膜を150℃/1時間＋250℃/2時間の条件で硬化さ
せ、膜厚20μmの硬化膜を形成した。この硬化膜には、
クラックの発生は見られず、またガラス基板によく接着
していた。またこの硬化膜はトルエン、テトラヒドロフ
ラン、ジイソプロピルエーテル、ジグライム及びメチル
イソブチルケトンに不溶であった。29.8 g (0.07 mol) of an epoxy group-containing disiloxane compound in which R 3 is a methyl group (molecular weight: 426) (methoxy group content: 0.28 mol) ) Ortho-titanate isopropyl ester 0.1g Toluene 300ml A mixture consisting of 300ml was heated in a nitrogen atmosphere at 100 ° C for 12 hours to react and mature. Then, toluene was distilled off at normal pressure and stripped at 150 ° C under vacuum for 1 hour. Was performed to obtain a solid. This was dissolved in a small amount of toluene and reprecipitated in a large amount of hexane.
After drying, 105 g (yield: 86.6%) of a white solid resin was obtained.
In the epoxy group-containing silicone resin thus obtained, the OH group of the silanol group-containing organopolysiloxane disappears from the measurement result of the IR spectrum, and the absorption of -CH 2- indicating the addition of the epoxy group-containing disiloxane compound is reduced. Admitted. The molecular weight of the resin by GPC was 17,000
And the content of epoxy group was 0.11 mol / 100 g. Next, the resin was dissolved in toluene to form a solution, which was applied on a glass substrate, dried at 100 ° C. for 30 minutes, and the obtained coating film was heated at 150 ° C./1 hour + 250 ° C./2 hours. The composition was cured to form a cured film having a thickness of 20 μm. In this cured film,
No crack was observed, and it was well adhered to the glass substrate. This cured film was insoluble in toluene, tetrahydrofuran, diisopropyl ether, diglyme and methyl isobutyl ketone.
【００２２】[0022]
【発明の効果】本発明のエポキシ基含有シリコーン樹脂
は、耐クラック性及び基板への接着性に優れた硬化物を
形成できるので、シリコーン樹脂としての従来の用途に
おける性能の改善及び用途拡大が可能となる。更に、こ
のエポキシ基含有シリコーン樹脂は、エポキシ基の機能
を生かした新規な用途にも期待でき、特に電気、電子及
び光学の分野での用途に有望である。The epoxy group-containing silicone resin of the present invention can form a cured product having excellent crack resistance and adhesiveness to a substrate, so that it is possible to improve the performance of conventional silicone resin applications and expand the range of applications. Becomes Furthermore, the epoxy group-containing silicone resin can be expected to be used for new applications utilizing the function of the epoxy group, and is particularly promising for applications in the fields of electricity, electronics and optics.
Claims (1)
ル基又はフェニル基を表し、ａは0.02〜2の正数であ
る。）で示される、分子量130〜5,000のシラノール基含
有オルガノポリシロキサンと、下記一般式（２）： 【化１】 で示されるエポキシ基含有ジシロキサン化合物とを縮合
重合させることにより得られたエポキシ基含有シリコー
ン樹脂。1. Average composition formula (1): (HO) a R 1 SiO (3-a) / 2 (1) (where R 1 is a methyl group, an ethyl group, a propyl group, a vinyl group or a phenyl group) Wherein a is a positive number of 0.02 to 2), and a silanol group-containing organopolysiloxane having a molecular weight of 130 to 5,000, and the following general formula (2): An epoxy group-containing silicone resin obtained by subjecting an epoxy group-containing disiloxane compound represented by the following to condensation polymerization.
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|---|---|---|---|
| JP21740899A JP3681582B2 (en) | 1999-07-30 | 1999-07-30 | Epoxy group-containing silicone resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21740899A JP3681582B2 (en) | 1999-07-30 | 1999-07-30 | Epoxy group-containing silicone resin |
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|---|---|
| JP2001040094A true JP2001040094A (en) | 2001-02-13 |
| JP3681582B2 JP3681582B2 (en) | 2005-08-10 |
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ID=16703741
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|---|---|---|---|
| JP21740899A Expired - Fee Related JP3681582B2 (en) | 1999-07-30 | 1999-07-30 | Epoxy group-containing silicone resin |
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| JP (1) | JP3681582B2 (en) |
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|---|---|---|---|---|
| WO2008090971A1 (en) * | 2007-01-25 | 2008-07-31 | Jsr Corporation | Terminally epoxidized polydimethylsiloxane, method for producing the same, and curable polysiloxane composition |
| WO2009072632A1 (en) * | 2007-12-07 | 2009-06-11 | Jsr Corporation | Curable composition, coating composition for optical device, led sealing material, and method for producing the same |
| WO2010026714A1 (en) * | 2008-09-03 | 2010-03-11 | 日本化薬株式会社 | Siloxane compound, curable resin composition, cured object obtained therefrom, and photosemiconductor element |
| JP2010059359A (en) * | 2008-09-05 | 2010-03-18 | Jsr Corp | Epoxy group-containing multifunctional polysiloxane and method for producing the same, and curable polysiloxane composition |
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1999
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Cited By (14)
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|---|---|---|---|---|
| WO2008090971A1 (en) * | 2007-01-25 | 2008-07-31 | Jsr Corporation | Terminally epoxidized polydimethylsiloxane, method for producing the same, and curable polysiloxane composition |
| JPWO2008090971A1 (en) * | 2007-01-25 | 2010-05-20 | Jsr株式会社 | Epoxy group-terminated polydimethylsiloxane, method for producing the same, and curable polysiloxane composition |
| WO2009072632A1 (en) * | 2007-12-07 | 2009-06-11 | Jsr Corporation | Curable composition, coating composition for optical device, led sealing material, and method for producing the same |
| JPWO2009072632A1 (en) * | 2007-12-07 | 2011-04-28 | Jsr株式会社 | Curable composition, optical element coating composition, LED sealing material, and method for producing the same |
| WO2010026714A1 (en) * | 2008-09-03 | 2010-03-11 | 日本化薬株式会社 | Siloxane compound, curable resin composition, cured object obtained therefrom, and photosemiconductor element |
| JP2010059359A (en) * | 2008-09-05 | 2010-03-18 | Jsr Corp | Epoxy group-containing multifunctional polysiloxane and method for producing the same, and curable polysiloxane composition |
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| US11089693B2 (en) | 2011-12-16 | 2021-08-10 | Prologium Technology Co., Ltd. | PCB structure with a silicone layer as adhesive |
| US20160249474A1 (en) * | 2012-12-13 | 2016-08-25 | Prologium Holding Inc. | Package structure of electronic modules with silicone sealing frame and the manufacturing method thereof |
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| US9312144B2 (en) | 2013-10-02 | 2016-04-12 | Shin-Etsu Chemical Co., Ltd. | Composition for forming a silicon-containing resist under layer film and patterning process |
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| EP2857467A1 (en) * | 2013-10-02 | 2015-04-08 | Shin-Etsu Chemical Co., Ltd. | Composition for forming a silicon-containing resist under layer film and patterning process |
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