JPH115844A - Organic resin modifying agent and organic resin - Google Patents
Organic resin modifying agent and organic resinInfo
- Publication number
- JPH115844A JPH115844A JP17655897A JP17655897A JPH115844A JP H115844 A JPH115844 A JP H115844A JP 17655897 A JP17655897 A JP 17655897A JP 17655897 A JP17655897 A JP 17655897A JP H115844 A JPH115844 A JP H115844A
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Silicon Polymers (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は有機樹脂改質剤およ
び有機樹脂に関し、詳しくは有機樹脂に高い反応性を付
与し得る有機樹脂改質剤および該有機樹脂改質剤により
改質された有機樹脂に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic resin modifier and an organic resin, and more particularly, to an organic resin modifier capable of imparting high reactivity to an organic resin and an organic resin modified by the organic resin modifier. About resin.
【0002】[0002]
【従来の技術】有機官能性基を有するオルガノポリシロ
キサンは、各種有機樹脂の撥水性,撥油性,耐溶剤性,
耐候性,耐熱性,離型性,成形加工性,耐衝撃性等の特
性を付与、向上させることから、樹脂改質剤として広く
利用されている。中でもアミノ基を有するオルガノポリ
シロキサンは、ポリイミド樹脂,ポリアミド樹脂等の熱
可塑性樹脂やエポキシ樹脂,フェノール樹脂等の熱硬化
性樹脂の改質剤として好適に使用されている。例えば、
分子鎖両末端にアミノプロピル基を有するジメチルポリ
シロキサンはポリイミド樹脂やポリアミド樹脂等の共重
合反応成分として使用されており(特開平7−2474
26号公報,特開平7−247427号公報,特開平7
−247428号公報参照)、さらに有機樹脂の反応性
を高める目的で、分子鎖両末端にアミノプロピル基を有
するジメチルシロキサン・メチルビニルシロキサン共重
合体が提案されている(特開平7−268098号公報
参照)。しかしこのジメチルシロキサン・メチルビニル
シロキサン共重合体により改質されたポリイミド樹脂で
あっても、ビニル基の反応性が十分でないため、例えば
ビニル基同士を反応させて架橋させた場合に、反応に長
時間要するという欠点があった。2. Description of the Related Art Organopolysiloxanes having an organic functional group are known for their water repellency, oil repellency, solvent resistance,
It is widely used as a resin modifier because it imparts and improves properties such as weather resistance, heat resistance, mold release properties, moldability, and impact resistance. Among them, an organopolysiloxane having an amino group is suitably used as a modifier for a thermoplastic resin such as a polyimide resin or a polyamide resin, or a thermosetting resin such as an epoxy resin or a phenol resin. For example,
Dimethylpolysiloxane having an aminopropyl group at both ends of the molecular chain is used as a copolymerization reaction component of a polyimide resin, a polyamide resin, or the like (Japanese Patent Laid-Open No. 7-2474).
26, JP-A-7-247427, JP-A-7-247427
JP-A-247428), and a dimethylsiloxane / methylvinylsiloxane copolymer having an aminopropyl group at both molecular chain terminals has been proposed for the purpose of further enhancing the reactivity of an organic resin (JP-A-7-268098). reference). However, even with a polyimide resin modified with this dimethylsiloxane / methylvinylsiloxane copolymer, the reactivity of vinyl groups is not sufficient. There was a disadvantage that it took time.
【0003】[0003]
【発明が解決しようとする課題】本発明者らは上記問題
点を解消すべく鋭意検討した結果、本発明に到達した。
即ち、本発明は、有機樹脂に高い反応性を付与し得る有
機樹脂改質剤および該有機樹脂改質剤により改質された
有機樹脂を提供することにある。The inventors of the present invention have made intensive studies to solve the above problems, and as a result, have reached the present invention.
That is, an object of the present invention is to provide an organic resin modifier capable of imparting high reactivity to an organic resin and an organic resin modified with the organic resin modifier.
【0004】[0004]
【課題を解決するための手段】本発明は、分子鎖両末端
に、式:−R1−NHR2または式:−R1−NH−R1−
NHR2(式中、R1は炭素原子数1〜9の二価炭化水素
基であり、R2は水素原子または炭素原子数1〜6の一
価炭化水素基である。)で示されるアミノ基を有し、側
鎖に炭素原子数4以上のアルケニル基を有するジオルガ
ノポリシロキサンを主剤とする有機樹脂改質剤および該
有機樹脂改質剤により改質された有機樹脂に関する。According to the present invention, a compound having the formula: -R 1 -NHR 2 or the formula: -R 1 -NH-R 1 -is provided at both ends of a molecular chain.
Amino represented by NHR 2 (wherein R 1 is a divalent hydrocarbon group having 1 to 9 carbon atoms, and R 2 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms) The present invention relates to an organic resin modifier mainly containing a diorganopolysiloxane having an alkenyl group having 4 or more carbon atoms in a side chain, and an organic resin modified by the organic resin modifier.
【0005】[0005]
【発明の実施の形態】最初に、本発明の有機樹脂改質剤
について説明する。本発明の有機樹脂改質剤は、分子鎖
両末端に、式:−R1−NHR2または式:−R1−NH
−R1−NHR2(式中、R1は炭素原子数1〜9の二価
炭化水素基であり、R2は水素原子または炭素原子数1
〜6の一価炭化水素基である。)で示されるアミノ基を
有し、側鎖に炭素原子数4以上のアルケニル基を有する
ジオルガノポリシロキサンを主剤とする。上式で示され
るアミノ基として具体的には、アミノプロピル基,アミ
ノエチルイミノプロピル基,t−ブチルイミノプロピル
基,n−ブチルイミノプロピル基,イソプロピルイミノ
プロピル基,フェニルイミノプロピル基,シクロヘキシ
ルアミノプロピル基が挙げられる。炭素原子数4以上の
アルケニル基としては末端に炭素−炭素二重結合を有す
るものが好ましく、具体的には、3−ブテニル基,4−
ペンテニル基,5−ヘキセニル基,6−ヘプテニル基,
7−オクタジエニル基,13−テトラデカジエニル基が
挙げられる。該アルケニル基の含有量はケイ素原子に結
合してなる全有機基中、0.1〜50モル%の範囲であ
ることが好ましく、さらに1〜50モル%の範囲である
ことがより好ましい。また、上記アミノ基およびアルケ
ニル基以外のケイ素原子に結合する基としては、脂肪族
不飽和結合を含まない一価炭化水素基やトリオルガノシ
ロキシ基が挙げられる。このようなジオルガノポリシロ
キサンとして具体的には、一般式:DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the organic resin modifier of the present invention will be described. The organic resin modifier of the present invention has the formula: —R 1 —NHR 2 or the formula: —R 1 —NH at both molecular chain terminals.
—R 1 —NHR 2 (wherein, R 1 is a divalent hydrocarbon group having 1 to 9 carbon atoms, and R 2 is a hydrogen atom or 1 carbon atom.
~ 6 monovalent hydrocarbon groups. The main component is a diorganopolysiloxane having an amino group represented by ()) and having an alkenyl group having 4 or more carbon atoms in a side chain. Specific examples of the amino group represented by the above formula include aminopropyl group, aminoethyliminopropyl group, t-butyliminopropyl group, n-butyliminopropyl group, isopropyliminopropyl group, phenyliminopropyl group, and cyclohexylaminopropyl. Groups. As the alkenyl group having 4 or more carbon atoms, a alkenyl group having a carbon-carbon double bond at a terminal is preferable, and specifically, a 3-butenyl group, 4-
A pentenyl group, a 5-hexenyl group, a 6-heptenyl group,
Examples thereof include a 7-octadienyl group and a 13-tetradecadienyl group. The content of the alkenyl group is preferably in the range of 0.1 to 50 mol%, more preferably in the range of 1 to 50 mol%, based on the total organic group bonded to the silicon atom. In addition, examples of the group bonded to a silicon atom other than the amino group and the alkenyl group include a monovalent hydrocarbon group containing no aliphatic unsaturated bond and a triorganosiloxy group. Specifically, such a diorganopolysiloxane has a general formula:
【化2】 で示される化合物が例示される。上式中、Rは脂肪族不
飽和結合を含まない同種または異種の一価炭化水素基で
あり、メチル基,エチル基,プロピル基,ブチル基,ペ
ンチル基,ヘキシル基のようなアルキル基;フェニル
基,トリル基,キシリル基のようなアリール基;ベンジ
ル基,フェニチル基のようなアラルキル基が例示され
る。Xは上式で示されるアミノ基であり、Yは前記した
炭素原子数4以上のアルケニル基である。mは0〜1,
000の整数であり、好ましくは0〜500の整数であ
る。nは1〜1,000の整数であり、好ましくは1〜
500の整数である。Embedded image Are exemplified. In the above formula, R is a monovalent or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, and an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; And aryl groups such as a tolyl group and a xylyl group; and aralkyl groups such as a benzyl group and a phenylyl group. X is an amino group represented by the above formula, and Y is the alkenyl group having 4 or more carbon atoms described above. m is 0-1,
000, preferably an integer of 0 to 500. n is an integer of 1 to 1,000, preferably 1 to 1,000.
It is an integer of 500.
【0006】このようなジオルガノポリシロキサンとし
ては、下記式で示される化合物が例示される。As such a diorganopolysiloxane, a compound represented by the following formula is exemplified.
【化3】 Embedded image
【化4】 Embedded image
【化5】 Embedded image
【化6】 Embedded image
【化7】 Embedded image
【化8】 Embedded image
【0007】このジオルガノポリシロキサンは、例え
ば、一般式:The diorganopolysiloxane has, for example, the general formula:
【化9】 (式中、RおよびYは前記と同じであり、rは3〜6の
整数である。)で示される環状のオルガノシロキサン、
または一般式:Embedded image (Wherein, R and Y are the same as described above, and r is an integer of 3 to 6).
Or the general formula:
【化10】 (式中、RおよびYは前記と同じであり、pは1〜80
の整数である。)で示される直鎖状のオルガノポリシロ
キサンと、一般式:Embedded image (Wherein, R and Y are the same as above, and p is 1 to 80)
Is an integer. ) And a linear organopolysiloxane represented by the general formula:
【化11】 (式中、RおよびXは前記と同じであり、qは0〜60
の整数である。)で示されるオルガノポリシロキサン
と、一般式:Embedded image (Wherein, R and X are the same as above, and q is 0 to 60)
Is an integer. ) And an organopolysiloxane represented by the general formula:
【化12】 (式中、Rおよびrは前記と同じである。)で示される
環状のオルガノシロキサンとを、塩基性触媒存在下に再
平衡化反応させることにより製造することができる。こ
のとき必要に応じて、一般式:Embedded image (Wherein, R and r are the same as described above), and a cyclic organosiloxane represented by the formula (1) is re-equilibrated in the presence of a basic catalyst. At this time, if necessary, the general formula:
【化13】 (式中、Rおよびpは前記と同じである。)で示される
オルガノポリシロキサンを加えてもよい。またこの反応
は、反応速度の点から、非プロトン系の極性溶媒の存在
下に行うことが好ましい。Embedded image (In the formula, R and p are the same as described above.) May be added. This reaction is preferably carried out in the presence of an aprotic polar solvent from the viewpoint of the reaction rate.
【0008】以上のような本発明の有機樹脂改質剤は、
ポリイミド樹脂やポリアミド樹脂等の熱可塑性樹脂やエ
ポキシ樹脂,フェノール樹脂,マレイミド樹脂等の熱硬
化性樹脂の樹脂改質剤として有用である。例えば、分子
鎖両末端のアミノ基の反応性を利用してポリイミド樹脂
やポリアミド樹脂の共重合反応成分として使用でき、さ
らに側鎖の長鎖アルケニル基の高い反応性を利用して、
該アルケニル基同士を反応させて有機樹脂を架橋させた
り、オルガノハイドロジェンポリシロキサンを付加反応
させたり、炭素−炭素二重結合を有する有機化合物を過
酸化物の存在下で反応させることができる。これにより
本発明の有機樹脂改質剤は有機樹脂に高い反応性を付与
し、かつ、優れた撥水性,撥油性,耐溶剤性,耐熱性,
離型性,耐衝撃性,接着性等の様々な特性を付与するこ
とができるという利点を有する。このような本発明の有
機樹脂改質剤は、例えば、塗料,成形材料,コーテイン
グ材料等に使用される各種有機樹脂の改質剤として好適
に使用される。The organic resin modifier of the present invention as described above comprises:
It is useful as a resin modifier for thermoplastic resins such as polyimide resins and polyamide resins, and thermosetting resins such as epoxy resins, phenol resins and maleimide resins. For example, by utilizing the reactivity of amino groups at both ends of the molecular chain, it can be used as a copolymerization reaction component of a polyimide resin or a polyamide resin, and further utilizing the high reactivity of a long-chain alkenyl group in a side chain,
The alkenyl groups can be reacted with each other to crosslink an organic resin, an addition reaction of an organohydrogenpolysiloxane, or an organic compound having a carbon-carbon double bond can be reacted in the presence of a peroxide. Thereby, the organic resin modifier of the present invention imparts high reactivity to the organic resin, and has excellent water repellency, oil repellency, solvent resistance, heat resistance,
There is an advantage that various characteristics such as releasability, impact resistance, and adhesiveness can be imparted. Such an organic resin modifier of the present invention is suitably used, for example, as a modifier for various organic resins used in paints, molding materials, coating materials and the like.
【0009】次に、本発明の有機樹脂について説明す
る。本発明の有機樹脂は、上記した本発明の有機樹脂改
質剤により改質されたものであり、該有機樹脂改質剤の
主剤であるジオルガノポリシロキサンが各種有機樹脂モ
ノマーと反応してシロキサン単位が樹脂中に導入された
共重合体や、該有機樹脂改質剤を単に添加配合してなる
有機樹脂組成物が挙げられる。使用される有機樹脂は特
に限定されないが、ポリイミド樹脂,ポリアミド樹脂,
ポリエステル樹脂等の熱可塑性樹脂;エポキシ樹脂,フ
ェノール樹脂,マレイミド樹脂等の熱硬化性樹脂が例示
される。これらの有機樹脂を単独で使用してもよく、ま
た2種類以上の混合物を使用してもよい。Next, the organic resin of the present invention will be described. The organic resin of the present invention has been modified with the above-described organic resin modifier of the present invention, and a diorganopolysiloxane which is a main component of the organic resin modifier reacts with various organic resin monomers to form a siloxane. Examples thereof include a copolymer having units introduced into a resin, and an organic resin composition obtained by simply adding and blending the organic resin modifier. Although the organic resin used is not particularly limited, polyimide resin, polyamide resin,
Thermoplastic resins such as polyester resins; thermosetting resins such as epoxy resins, phenol resins, and maleimide resins are exemplified. These organic resins may be used alone, or a mixture of two or more kinds may be used.
【0010】このような本発明の有機樹脂としては、例
えば、式:The organic resin of the present invention includes, for example, a compound represented by the following formula:
【化14】 で示される構成単位0.1〜100モル%と式:Embedded image And 0.1 to 100 mol% of a structural unit represented by the formula:
【化15】 {上式中、Ar1およびAr2は少なくとも1個の芳香族
環を有する四価の有機基であり、Ar3は少なくとも1
個の芳香族環を有する二価の有機基であり、Bは式:−
R1−または式:−R1−NH−R1−で示される基(式
中、R1は前記と同じである。)であり、R,Y,mお
よびnは前記と同じである。}で示される構成単位9
9.9〜0モル%からなるポリイミド樹脂や、式:Embedded image In the above formula, Ar 1 and Ar 2 are tetravalent organic groups having at least one aromatic ring, and Ar 3 is at least 1
Is a divalent organic group having three aromatic rings, and B has the formula:-
R 1 — or a group represented by the formula: —R 1 —NH—R 1 — (wherein R 1 is the same as described above), and R, Y, m, and n are the same as described above. Structural unit 9 indicated by}
9.9 to 0 mol% of a polyimide resin or a compound represented by the formula:
【化16】 で示される構成単位0.1〜100モル%と式:Embedded image And 0.1 to 100 mol% of a structural unit represented by the formula:
【化17】 (上式中、R3,R4,R5は二価の有機基であり、R,
Y,m,nおよびBは前記と同じである。)で示される
構成単位99.9〜0モル%からなるポリアミド樹脂
や、一般のエポキシ樹脂に上記有機樹脂改質剤を添加配
合してなるエポキシ樹脂組成物が挙げられる。上式中、
Ar1およびAr2で示される四価の有機基としては、下
記式で示される基が例示される。Embedded image (Wherein R 3 , R 4 , and R 5 are divalent organic groups;
Y, m, n and B are the same as described above. And the epoxy resin composition obtained by adding and blending the organic resin modifier to a general epoxy resin. In the above formula,
Examples of the tetravalent organic group represented by Ar 1 and Ar 2 include a group represented by the following formula.
【化18】 Ar3で示される二価の有機基としては、下記式で示さ
れる基が例示される。Embedded image Examples of the divalent organic group represented by Ar 3 include a group represented by the following formula.
【化19】 また、後者のエポキシ樹脂組成物の場合、エポキシ樹脂
100重量部に対して本発明の有機樹脂改質剤が0.1
〜200重量部の範囲で配合されることが好ましい。Embedded image In the case of the latter epoxy resin composition, the organic resin modifier of the present invention is used in an amount of 0.1 part by weight per 100 parts by weight of the epoxy resin.
It is preferable to mix in the range of -200 parts by weight.
【0011】さらに本発明の有機樹脂には補強性充填剤
や各種添加剤を配合することができる。補強性充填剤と
しては、ガラス繊維,炭素繊維,ガラスクロス,炭酸カ
ルシウム,マイカ,タルクが例示される。各種添加剤と
しては、例えば、強度改良剤,酸化防止剤,紫外線吸収
剤,耐光安定剤,耐熱安定剤,可塑剤,発泡剤,結晶核
剤,滑剤,帯電防止剤,導電性付与剤,顔料や染料など
の着色剤,相溶化剤,架橋剤,難燃剤,防カビ剤,低収
縮剤,増粘剤,離型剤,防曇剤,ブルーイング剤,カッ
プリング剤が挙げられる。The organic resin of the present invention may further contain a reinforcing filler and various additives. Examples of the reinforcing filler include glass fiber, carbon fiber, glass cloth, calcium carbonate, mica, and talc. Examples of various additives include a strength improver, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, a foaming agent, a crystal nucleating agent, a lubricant, an antistatic agent, a conductivity imparting agent, and a pigment. Coloring agents such as dyes and dyes, compatibilizers, crosslinking agents, flame retardants, mildewproofing agents, low-shrinking agents, thickeners, release agents, antifogging agents, bluing agents, and coupling agents.
【0012】このような本発明の有機樹脂は反応性が高
く、かつ、撥水性,撥油性,耐溶剤性,耐熱性,離型
性,耐衝撃性,接着性,寸法安定性等に優れるという利
点を有する。The organic resin of the present invention has high reactivity and is excellent in water repellency, oil repellency, solvent resistance, heat resistance, mold release, impact resistance, adhesiveness, dimensional stability and the like. Has advantages.
【0013】[0013]
【実施例】以下、本発明を実施例にて詳細に説明する。
実施例中、粘度は25℃における測定値である。The present invention will be described below in detail with reference to examples.
In the examples, the viscosity is a value measured at 25 ° C.
【0014】[0014]
【参考例1】攪拌機,還流器,温度計を備えた200ミ
リリットルフラスコに、式:[Reference Example 1] In a 200 ml flask equipped with a stirrer, a reflux condenser, and a thermometer, the formula:
【化20】 で示されるジシロキサン20.0グラム,式:Embedded image 20.0 g of a disiloxane represented by the formula:
【化21】 で示される環状シロキサン80.2グラムを投入した。
これに触媒として水酸化カリウム200ppmを添加し
て、140〜150℃で8時間反応させた。反応終了
後、酢酸300ppmを添加して触媒を中和して100
℃で30分間攪拌した。次いでこの反応混合物から、低
分子化合物を150℃/10mmHgで留去した後、濾
過により酢酸を除去して、粘度35センチストークスの
淡黄色透明の液体95グラムを得た。この液体をゲル透
過クロマトグラフィー(以下、GPC),核磁気共鳴分
析(以下、NMR)および赤外分光分析(以下、IR)
により分析したところ、下記平均組成式で示されるジオ
ルガノポリシロキサンであることが判明した。Embedded image 80.2 g of the cyclic siloxane represented by
To this, 200 ppm of potassium hydroxide was added as a catalyst and reacted at 140 to 150 ° C. for 8 hours. After completion of the reaction, the catalyst was neutralized by adding 300 ppm of acetic acid to 100
Stirred at C for 30 minutes. Next, the low molecular weight compound was distilled off from the reaction mixture at 150 ° C./10 mmHg, and then acetic acid was removed by filtration to obtain 95 g of a pale yellow transparent liquid having a viscosity of 35 cSt. This liquid is subjected to gel permeation chromatography (hereinafter, GPC), nuclear magnetic resonance analysis (hereinafter, NMR) and infrared spectroscopy (hereinafter, IR)
As a result, it was found to be a diorganopolysiloxane represented by the following average composition formula.
【化22】 Embedded image
【0015】[0015]
【参考例2】攪拌機,還流器,温度計を備えた200ミ
リリットルフラスコに、式:[Reference Example 2] In a 200 ml flask equipped with a stirrer, a reflux condenser, and a thermometer, the formula:
【化23】 で示されるジシロキサン28.0グラム,式:Embedded image 28.0 g of a disiloxane represented by the formula:
【化24】 で示される環状シロキサン41.8グラム,式:Embedded image 41.8 g of a cyclic siloxane represented by the formula:
【化25】 で示される環状シロキサン32.0グラムを投入した。
これに触媒として水酸化カリウム200ppmを添加し
て、140〜150℃で8時間反応させた。反応終了
後、酢酸300ppmを添加して触媒を中和して100
℃で30分間攪拌した。次いでこの反応混合物から、低
分子化合物を150℃/10mmHgで留去した後、濾
過により酢酸を除去して、粘度15センチストークスの
淡黄色透明の液体93グラムを得た。この液体を、GP
C,NMRおよびIRにより分析したところ、下記平均
組成式で示されるジオルガノポリシロキサンであること
が判明した。Embedded image Was charged.
To this, 200 ppm of potassium hydroxide was added as a catalyst and reacted at 140 to 150 ° C. for 8 hours. After completion of the reaction, the catalyst was neutralized by adding 300 ppm of acetic acid to 100
Stirred at C for 30 minutes. Next, low-molecular compounds were distilled off from the reaction mixture at 150 ° C./10 mmHg, and acetic acid was removed by filtration to obtain 93 g of a pale yellow transparent liquid having a viscosity of 15 centistokes. This liquid is GP
Analysis by C, NMR and IR revealed that it was a diorganopolysiloxane represented by the following average composition formula.
【化26】 Embedded image
【0016】[0016]
【実施例1】窒素気流下、撹拌機,滴下ロート,温度計
を備えた500mlの4つ口フラスコに、3,3',4,
4'−ベンゾフェノンテトラカルボン酸2無水物16.1
1gを投入し、乾燥したN−メチルピロリドン120g
を加えて溶解した。次いでこれに、室温下、参考例1で
得られたジオルガノポリシロキサン16.80gを徐々
に滴下した。滴下終了後、1時間撹拌を行った。次いで
これに、3−アミノフェニルサルホン9.06gを乾燥
したN−メチルピロリドン80gに溶解したものを、氷
冷下にて徐々に滴下した。滴下終了後、氷冷下で1時間
攪拌し、さらに室温下で4時間撹拌して、下記式(A−
1)および(B−1)で表される構成単位からなるポリ
アミック酸のN−メチルピロリドン溶液を得た。 式(A−1):Example 1 Under a nitrogen gas stream, 3,3 ′, 4,
4'-benzophenonetetracarboxylic dianhydride 16.1
1 g, and 120 g of dried N-methylpyrrolidone
Was added and dissolved. Then, at room temperature, 16.80 g of the diorganopolysiloxane obtained in Reference Example 1 was gradually added dropwise at room temperature. After completion of the dropwise addition, stirring was performed for 1 hour. Next, a solution prepared by dissolving 9.06 g of 3-aminophenylsulfone in 80 g of dried N-methylpyrrolidone was gradually dropped under ice-cooling. After completion of the dropwise addition, the mixture was stirred for 1 hour under ice-cooling, and further stirred for 4 hours at room temperature.
An N-methylpyrrolidone solution of the polyamic acid comprising the structural units represented by 1) and (B-1) was obtained. Formula (A-1):
【化27】 式(B−1):Embedded image Formula (B-1):
【化28】 上記構成単位の共重合比(モル%)は、(A−1):
(B−1)=27:73であった。次に、フラスコにD
ean Stark還流管を取り付けて、キシレン10
0gを追加した。この反応溶液を130〜190℃で6
時間還流脱水して、下記式(A−2)および(B−2)
で表される構成単位からなるポリイミド樹脂のN−メチ
ルピロリドン溶液を得た。 式(A−2):Embedded image The copolymerization ratio (mol%) of the above structural units is (A-1):
(B-1) = 27: 73. Next, add D to the flask.
Attach an ean Stark reflux tube and add xylene 10
0 g was added. This reaction solution is heated at 130 to 190 ° C. for 6 hours.
After dewatering under reflux for a time, the following formulas (A-2) and (B-2)
A N-methylpyrrolidone solution of a polyimide resin consisting of the structural units represented by was obtained. Formula (A-2):
【化29】 式(B−2):Embedded image Formula (B-2):
【化30】 上記構成単位の共重合比(モル%)は、(A−2):
(B−2)=27:73であった。このようにして得ら
れたポリイミド樹脂のN−メチルピロリドン溶液の固有
粘度を測定したところ、0.45dl/gであった。ま
た、得られたポリイミド樹脂に、窒素気流下、トリエト
キシシラン12.42gと、塩化白金酸−オレフィン錯
体をポリイミド樹脂に対する白金金属量が50ppmと
なる量配合し、50℃にて加熱撹拌した。2時間および
4時間経過後にガラスシリンジを用いて試料を抜き出
し、ガスクロマトグラフィーにてトリエトキシシランの
消費量を測定して、反応率(付加反応の進行度合)を追
跡した。その結果を表1に示した。Embedded image The copolymerization ratio (mol%) of the above structural units is (A-2):
(B-2) = 27: 73. When the intrinsic viscosity of the N-methylpyrrolidone solution of the polyimide resin thus obtained was measured, it was 0.45 dl / g. Further, 12.42 g of triethoxysilane and chloroplatinic acid-olefin complex were blended with the obtained polyimide resin under a nitrogen stream in such an amount that the amount of platinum metal relative to the polyimide resin became 50 ppm, followed by heating and stirring at 50 ° C. After a lapse of 2 hours and 4 hours, a sample was taken out using a glass syringe, the consumption of triethoxysilane was measured by gas chromatography, and the reaction rate (degree of progress of the addition reaction) was followed. The results are shown in Table 1.
【0017】[0017]
【実施例2】窒素気流下、撹拌機,滴下ロート,温度計
を備えた500mlの4つ口フラスコに、3,3',4,
4'−ベンゾフェノンテトラカルボン酸2無水物16.1
1gを投入し、乾燥したN−メチルピロリドン120g
を加えて溶解した。次いでこれに、室温下、参考例1で
得られたジオルガノポリシロキサン20.04gを徐々
に滴下した。滴下終了後、1時間撹拌を行った。次いで
これに、2,2'−ビス(4−アミノフェノキシフェニ
ル)プロパン13.92gを乾燥したN−メチルピロリ
ドン80gに溶解したものを、氷冷下にて徐々に滴下し
た。滴下終了後、氷冷下で1時間攪拌し、さらに室温下
で4時間撹拌して、下記式(A−1)および(B−1)
で表される構成単位からなるポリアミック酸のN−メチ
ルピロリドン溶液を得た。 式(A−1):Example 2 Under a nitrogen stream, 3,3 ', 4,3
4'-benzophenonetetracarboxylic dianhydride 16.1
1 g, and 120 g of dried N-methylpyrrolidone
Was added and dissolved. Then, at room temperature, 20.04 g of the diorganopolysiloxane obtained in Reference Example 1 was gradually added dropwise at room temperature. After completion of the dropwise addition, stirring was performed for 1 hour. Next, a solution prepared by dissolving 13.92 g of 2,2′-bis (4-aminophenoxyphenyl) propane in 80 g of dried N-methylpyrrolidone was gradually dropped under ice cooling. After completion of the dropwise addition, the mixture was stirred for 1 hour under ice-cooling, and further for 4 hours at room temperature to obtain the following formulas (A-1) and (B-1)
Thus, an N-methylpyrrolidone solution of a polyamic acid comprising the structural unit represented by the formula was obtained. Formula (A-1):
【化31】 式(B−1):Embedded image Formula (B-1):
【化32】 上記構成単位の共重合比(モル%)は、(A−1):
(B−1)=32:68であった。次に、フラスコにD
ean Stark還流管を取り付けて、キシレン10
0gを追加した。この反応溶液を130〜190℃で6
時間還流脱水して、下記式(A−2)および(B−2)
で表される構成単位からなるポリイミド樹脂のN−メチ
ルピロリドン溶液を得た。 式(A−2):Embedded image The copolymerization ratio (mol%) of the above structural units is (A-1):
(B-1) = 32: 68. Next, add D to the flask.
Attach an ean Stark reflux tube and add xylene 10
0 g was added. This reaction solution is heated at 130 to 190 ° C. for 6 hours.
After dewatering under reflux for a time, the following formulas (A-2) and (B-2)
A N-methylpyrrolidone solution of a polyimide resin consisting of the structural units represented by was obtained. Formula (A-2):
【化33】 式(B−2):Embedded image Formula (B-2):
【化34】 上記構成単位の共重合比(モル%)は、(A−2):
(B−2)=32:68であった。このようにして得ら
れたポリイミド樹脂のN−メチルピロリドン溶液の固有
粘度を測定したところ、0.42dl/gであった。ま
た、得られたポリイミド樹脂に、窒素気流下、トリエト
キシシラン14.81gと、塩化白金酸−オレフィン錯
体をポリイミド樹脂に対する白金金属量が50ppmと
なる量配合し、50℃にて加熱撹拌した。2時間および
4時間経過後にガラスシリンジを用いて試料を抜き出
し、ガスクロマトグラフィーにてトリエトキシシランの
消費量を測定して、反応率(付加反応の進行度合)を追
跡した。その結果を表1に示した。Embedded image The copolymerization ratio (mol%) of the above structural units is (A-2):
(B-2) = 32: 68. When the intrinsic viscosity of the N-methylpyrrolidone solution of the polyimide resin thus obtained was measured, it was 0.42 dl / g. In addition, 14.81 g of triethoxysilane and a chloroplatinic acid-olefin complex were added to the obtained polyimide resin in a nitrogen stream in such an amount that the amount of platinum metal relative to the polyimide resin became 50 ppm, and the mixture was heated and stirred at 50 ° C. After a lapse of 2 hours and 4 hours, a sample was taken out using a glass syringe, the consumption of triethoxysilane was measured by gas chromatography, and the reaction rate (degree of progress of the addition reaction) was followed. The results are shown in Table 1.
【0018】[0018]
【実施例3】窒素気流下、撹拌機、滴下ロート、温度計
を備えた500mlの4つ口フラスコに、3,3',4,
4'−ベンゾフェノンテトラカルボン酸2無水物16.1
1gを投入し、乾燥したN−メチルピロリドン120g
を加えて溶解した。次いでこれに、室温下、参考例2で
得られたジオルガノポリシロキサン18.71gを徐々
に滴下した。滴下終了後、1時間撹拌を行った。次いで
これに、2,2'−ビス(4−アミノフェノキシフェニ
ル)プロパン12.03gを乾燥したN−メチルピロリ
ドン80gに溶解したものを、氷冷下にて徐々に滴下し
た。滴下終了後、氷冷下で1時間撹拌し、さらに室温下
で4時間撹拌して、下記式(A−1)および(B−1)
で表される構成単位からなるポリアミック酸のN−メチ
ルピロリドン溶液を得た。 式(A−1):Example 3 Under a nitrogen stream, a 3,3 ′, 4,4
4'-benzophenonetetracarboxylic dianhydride 16.1
1 g, and 120 g of dried N-methylpyrrolidone
Was added and dissolved. Next, 18.71 g of the diorganopolysiloxane obtained in Reference Example 2 was gradually dropped at room temperature. After completion of the dropwise addition, stirring was performed for 1 hour. Next, a solution of 12.2 g of 2,2′-bis (4-aminophenoxyphenyl) propane dissolved in 80 g of dried N-methylpyrrolidone was gradually dropped under ice cooling. After completion of the dropwise addition, the mixture was stirred for 1 hour under ice-cooling, and further for 4 hours at room temperature to obtain the following formulas (A-1) and (B-1)
Thus, an N-methylpyrrolidone solution of a polyamic acid comprising the structural unit represented by the formula was obtained. Formula (A-1):
【化35】 式(B−1):Embedded image Formula (B-1):
【化36】 上記構成単位の共重合比(モル%)は、(A−1):
(B−1)=41:59であった。次に、フラスコにD
ean Stark還流管を取り付けて、キシレン10
0gを追加した。この反応溶液を130〜190℃で6
時間還流脱水して、下記式(A−2)および(B−2)
で表される構成単位からなるポリイミド樹脂のN−メチ
ルピロリドン溶液を得た。 式(A−2):Embedded image The copolymerization ratio (mol%) of the above structural units is (A-1):
(B-1) = 41: 59. Next, add D to the flask.
Attach an ean Stark reflux tube and add xylene 10
0 g was added. This reaction solution is heated at 130 to 190 ° C for 6 hours.
After dewatering under reflux for a time, the following formulas (A-2) and (B-2)
A N-methylpyrrolidone solution of a polyimide resin consisting of the structural units represented by was obtained. Formula (A-2):
【化37】 式(B−2):Embedded image Formula (B-2):
【化38】 上記構成単位の共重合比(モル%)は、(A−2):
(B−2)=41:59であった。このようにして得ら
れたポリイミド樹脂のN−メチルピロリドン溶液の固有
粘度を測定したところ、0.47dl/gであった。ま
た、得られたポリイミド樹脂に、窒素気流下、トリエト
キシシラン5.44gと、塩化白金酸−オレフィン錯体
をポリイミド樹脂に対する白金金属量が20ppmとな
る量配合し、60℃にて加熱撹拌した。2時間および4
時間経過後にガラスシリンジを用いて試料を抜き出し、
ガスクロマトグラフィーにてトリエトキシシランの消費
量を測定して、反応率(付加反応の進行度合)を追跡し
た。その結果を表1に示した。Embedded image The copolymerization ratio (mol%) of the above structural units is (A-2):
(B-2) = 41: 59. The intrinsic viscosity of the N-methylpyrrolidone solution of the polyimide resin thus obtained was measured and found to be 0.47 dl / g. In addition, 5.44 g of triethoxysilane and a chloroplatinic acid-olefin complex were added to the obtained polyimide resin under a nitrogen stream in such an amount that the amount of platinum metal to the polyimide resin became 20 ppm, and the mixture was heated and stirred at 60 ° C. 2 hours and 4
After the elapse of time, extract the sample using a glass syringe,
The consumption of triethoxysilane was measured by gas chromatography, and the reaction rate (degree of progress of the addition reaction) was followed. The results are shown in Table 1.
【0019】[0019]
【比較例1】窒素気流下、撹拌機,滴下ロート,温度計
を備えた500mlの4つ口フラスコに、3,3',4,
4'−ベンゾフェノンテトラカルボン酸2無水物16.1
1gを投入し、乾燥したN−メチルピロリドン120g
を加えて溶解した。次いでこれに、室温下、式:[Comparative Example 1] Under a nitrogen stream, a 3,3 ', 4,3,3,4,4
4'-benzophenonetetracarboxylic dianhydride 16.1
1 g, and 120 g of dried N-methylpyrrolidone
Was added and dissolved. Then, at room temperature, the formula:
【化39】 で表わされるジオルガノポリシロキサン15.93gを
徐々に滴下した。滴下終了後、1時間撹拌を行った。次
いでこれに、3−アミノフェニルサルホン7.77gを
乾燥したN−メチルピロリドン80gに溶解したもの
を、氷冷下にて徐々に滴下した。滴下終了後、氷冷下で
1時間撹拌し、さらに室温下で4時間撹拌して、下記式
(A−1)および(B−1)で表される構成単位からな
るポリアミック酸のN−メチルピロリドン溶液を得た。 式(A−1):Embedded image 15.93 g of a diorganopolysiloxane represented by the formula was gradually added dropwise. After completion of the dropwise addition, stirring was performed for 1 hour. Next, a solution prepared by dissolving 7.77 g of 3-aminophenylsulfone in 80 g of dried N-methylpyrrolidone was gradually dropped under ice-cooling. After completion of the dropwise addition, the mixture is stirred for 1 hour under ice-cooling and further for 4 hours at room temperature to obtain N-methyl of a polyamic acid composed of structural units represented by the following formulas (A-1) and (B-1). A pyrrolidone solution was obtained. Formula (A-1):
【化40】 式(B−1):Embedded image Formula (B-1):
【化41】 上記構成単位の共重合比(モル%)は、(A−1):
(B−1)=37:63であった。次に、フラスコにD
ean Stark還流管を取り付けて、キシレン10
0gを追加した。この反応溶液を130〜190℃で6
時間還流脱水して、下記式(A−2)および(B−2)
で表される構成単位からなるポリイミド樹脂のN−メチ
ルピロリドン溶液を得た。 式(A−2):Embedded image The copolymerization ratio (mol%) of the above structural units is (A-1):
(B-1) = 37: 63. Next, add D to the flask.
Attach an ean Stark reflux tube and add xylene 10
0 g was added. This reaction solution is heated at 130 to 190 ° C. for 6 hours.
After dewatering under reflux for a time, the following formulas (A-2) and (B-2)
A N-methylpyrrolidone solution of a polyimide resin consisting of the structural units represented by was obtained. Formula (A-2):
【化42】 式(B−2):Embedded image Formula (B-2):
【化43】 上記構成単位の共重合比(モル%)は、(A−2):
(B−2)=37:63であった。このようにして得ら
れたポリイミド樹脂のN−メチルピロリドン溶液の固有
粘度を測定したところ、0.47dl/gであった。ま
た、得られたポリイミド樹脂に、窒素気流下、トリエト
キシシラン5.44gと、塩化白金酸−オレフィン錯体
をポリイミド樹脂に対する白金金属量が50ppmとな
る量配合し、50℃にて加熱撹拌した。2時間および4
時間経過後にガラスシリンジを用いて試料を抜き出し、
ガスクロマトグラフィーにてトリエトキシシランの消費
量を測定して、反応率(付加反応の進行度合)を追跡し
た。その結果を表1に示した。Embedded image The copolymerization ratio (mol%) of the above structural units is (A-2):
(B-2) = 37: 63. The intrinsic viscosity of the N-methylpyrrolidone solution of the polyimide resin thus obtained was measured and found to be 0.47 dl / g. In addition, 5.44 g of triethoxysilane and an amount of chloroplatinic acid-olefin complex were mixed with the obtained polyimide resin in a nitrogen stream so that the amount of platinum metal relative to the polyimide resin became 50 ppm, and the mixture was heated and stirred at 50 ° C. 2 hours and 4
After the elapse of time, extract the sample using a glass syringe,
The consumption of triethoxysilane was measured by gas chromatography, and the reaction rate (degree of progress of the addition reaction) was followed. The results are shown in Table 1.
【0020】[0020]
【比較例2】窒素気流下、撹拌機,滴下ロート,温度計
を備えた500mlの4つ口フラスコに、3,3',4,
4'−ベンゾフェノンテトラカルボン酸2無水物16.1
1gを投入し、乾燥したN−メチルピロリドン120g
を加えて溶解した。次いでこれに、室温下、式:[Comparative Example 2] Under a nitrogen stream, a 3,3 ', 4,4,3,4,4
4'-benzophenonetetracarboxylic dianhydride 16.1
1 g, and 120 g of dried N-methylpyrrolidone
Was added and dissolved. Then, at room temperature, the formula:
【化44】 で表されるジオルガノポリシロキサン18.49gを徐
々に滴下した。滴下終了後、1時間撹拌を行った。次い
でこれに、2,2'−ビス(4−アミノフェノキシフェニ
ル)プロパン11.62gを乾燥したN−メチルピロリ
ドン80gに溶解したものを、氷冷下にて徐々に滴下し
た。滴下終了後、氷冷下で1時間撹拌し、さらに室温下
で4時間撹拌して、下記式(A−1)および(B−1)
で表される構成単位からなるポリアミック酸のN−メチ
ルピロリドン溶液を得た。 式(A−1):Embedded image 18.49 g of a diorganopolysiloxane represented by the formula was gradually added dropwise. After completion of the dropwise addition, stirring was performed for 1 hour. Next, a solution of 11.2 g of 2,2′-bis (4-aminophenoxyphenyl) propane dissolved in 80 g of dried N-methylpyrrolidone was gradually dropped under ice cooling. After completion of the dropwise addition, the mixture was stirred for 1 hour under ice-cooling, and further for 4 hours at room temperature to obtain the following formulas (A-1) and (B-1)
Thus, an N-methylpyrrolidone solution of a polyamic acid comprising the structural unit represented by the formula was obtained. Formula (A-1):
【化45】 式(B−1):Embedded image Formula (B-1):
【化46】 上記構成単位の共重合比(モル%)は、(A−1):
(B−1)=43:57であった。次に、フラスコにD
ean Stark還流管を取り付けて、キシレン10
0gを追加した。この反応溶液を130〜190℃で6
時間還流脱水して、下記式(A−2)および(B−2)
で表される構成単位からなるポリイミド樹脂のN−メチ
ルピロリドン溶液を得た。 式(A−2):Embedded image The copolymerization ratio (mol%) of the above structural units is (A-1):
(B-1) = 43: 57. Next, add D to the flask.
Attach an ean Stark reflux tube and add xylene 10
0 g was added. This reaction solution is heated at 130 to 190 ° C. for 6 hours.
After dewatering under reflux for a time, the following formulas (A-2) and (B-2)
A N-methylpyrrolidone solution of a polyimide resin consisting of the structural units represented by was obtained. Formula (A-2):
【化47】 式(B−2):Embedded image Formula (B-2):
【化48】 上記構成単位の共重合比(モル%)は、(A−2):
(B−2)=43:57であった。このようにして得ら
れたポリイミド樹脂のN−メチルピロリドン溶液の固有
粘度を測定したところ、0.47dl/gであった。ま
た、得られたポリイミド樹脂に、窒素気流下、トリエト
キシシラン5.44gと、塩化白金酸−オレフィン錯体
をポリイミド樹脂に対する白金金属量が50ppmとな
る量配合し、50℃にて加熱撹拌した。2時間および4
時間経過後にガラスシリンジを用いて試料を抜き出し、
ガスクロマトグラフィーにてトリエトキシシランの消費
量を測定して、反応率(付加反応の進行度合)を追跡し
た。その結果を表1に示した。Embedded image The copolymerization ratio (mol%) of the above structural units is (A-2):
(B-2) = 43: 57. The intrinsic viscosity of the N-methylpyrrolidone solution of the polyimide resin thus obtained was measured and found to be 0.47 dl / g. In addition, 5.44 g of triethoxysilane and an amount of chloroplatinic acid-olefin complex were mixed with the obtained polyimide resin in a nitrogen stream so that the amount of platinum metal relative to the polyimide resin became 50 ppm, and the mixture was heated and stirred at 50 ° C. 2 hours and 4
After the elapse of time, extract the sample using a glass syringe,
The consumption of triethoxysilane was measured by gas chromatography, and the reaction rate (degree of progress of the addition reaction) was followed. The results are shown in Table 1.
【0021】[0021]
【比較例3】窒素気流下、撹拌機,滴下ロート,温度計
を備えた500mlの4つ口フラスコに、3,3',4,
4'−ベンゾフェノンテトラカルボン酸2無水物16.1
1gを投入し、乾燥したN−メチルピロリドン120g
を加えて溶解した。次いでこれに、室温下、式:[Comparative Example 3] Under a nitrogen stream, a 3,3 ', 4,4
4'-benzophenonetetracarboxylic dianhydride 16.1
1 g, and 120 g of dried N-methylpyrrolidone
Was added and dissolved. Then, at room temperature, the formula:
【化49】 で表わされるジオルガノポリシロキサン18.13gを
徐々に滴下した。滴下終了後、1時間撹拌を行った。次
いでこれに、2,2'−ビス(4−アミノフェノキシフェ
ニル)プロパン11.12gを乾燥したN−メチルピロ
リドン80gに溶解したものを、氷冷下にて徐々に滴下
した。滴下終了後、氷冷下で1時間撹拌し、さらに室温
下で4時間撹拌して、下記式(A−1)および(B−
1)で表される構成単位からなるポリアミック酸のN−
メチルピロリドン溶液を得た。 式(A−1):Embedded image 18.13 g of a diorganopolysiloxane represented by the formula was gradually added dropwise. After completion of the dropwise addition, stirring was performed for 1 hour. Next, a solution prepared by dissolving 11.12 g of 2,2′-bis (4-aminophenoxyphenyl) propane in 80 g of dried N-methylpyrrolidone was gradually dropped under ice cooling. After completion of the dropwise addition, the mixture was stirred for 1 hour under ice-cooling and further for 4 hours at room temperature to obtain the following formulas (A-1) and (B-
N- of the polyamic acid comprising the structural unit represented by 1)
A methylpyrrolidone solution was obtained. Formula (A-1):
【化50】 式(B−1):Embedded image Formula (B-1):
【化51】 上記構成単位の共重合比(モル%)は、(A−1):
(B−1)=46:54であった。次に、フラスコにD
ean Stark還流管を取り付けて、キシレン10
0gを追加した。この反応溶液を130〜190℃で6
時間還流脱水して、下記式(A−2)および(B−2)
で表される構成単位からなるポリイミド樹脂のN−メチ
ルピロリドン溶液を得た。 式(A−2):Embedded image The copolymerization ratio (mol%) of the above structural units is (A-1):
(B-1) = 46: 54. Next, add D to the flask.
Attach an ean Stark reflux tube and add xylene 10
0 g was added. This reaction solution is heated at 130 to 190 ° C. for 6 hours.
After dewatering under reflux for a time, the following formulas (A-2) and (B-2)
A N-methylpyrrolidone solution of a polyimide resin consisting of the structural units represented by was obtained. Formula (A-2):
【化52】 式(B−2):Embedded image Formula (B-2):
【化53】 上記構成単位の共重合比(モル%)は、(A−2):
(B−2)=46:54であった。このようにして得ら
れたポリイミド樹脂のN−メチルピロリドン溶液の固有
粘度を測定したところ、0.47dl/gであった。ま
た、得られたポリイミド樹脂に、窒素気流下、トリエト
キシシラン5.44gと、塩化白金酸−オレフィン錯体
をポリイミド樹脂に対する白金金属量が20ppmとな
る量配合し、60℃にて加熱撹拌した。2時間および4
時間経過後にガラスシリンジを用いて試料を抜き出し、
ガスクロマトグラフィーにてトリエトキシシランの消費
量を測定して、反応率(付加反応の進行度合)を追跡し
た。その結果を表1に示した。Embedded image The copolymerization ratio (mol%) of the above structural units is (A-2):
(B-2) = 46: 54. The intrinsic viscosity of the N-methylpyrrolidone solution of the polyimide resin thus obtained was measured and found to be 0.47 dl / g. In addition, 5.44 g of triethoxysilane and a chloroplatinic acid-olefin complex were added to the obtained polyimide resin under a nitrogen stream in such an amount that the amount of platinum metal to the polyimide resin became 20 ppm, and the mixture was heated and stirred at 60 ° C. 2 hours and 4
After the elapse of time, extract the sample using a glass syringe,
The consumption of triethoxysilane was measured by gas chromatography, and the reaction rate (degree of progress of the addition reaction) was followed. The results are shown in Table 1.
【0022】[0022]
【表1】 [Table 1]
【0023】[0023]
【発明の効果】以上のような本発明の有機樹脂改質剤は
分子鎖両末端にアミノ基を有し、側鎖に長鎖アルケニル
基を有するジオルガノポリシロキサンを主剤とするもの
であり、これにより該有機樹脂改質剤により改質された
有機樹脂は高い反応性を示すという利点を有する。The organic resin modifier of the present invention as described above is mainly composed of a diorganopolysiloxane having an amino group at both ends of a molecular chain and a long-chain alkenyl group in a side chain. Thereby, the organic resin modified by the organic resin modifier has an advantage of exhibiting high reactivity.
【図1】 図1は参考例1で得られたジオルガノポリシ
ロキサンのIRチャートである。FIG. 1 is an IR chart of the diorganopolysiloxane obtained in Reference Example 1.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 FI // C08L 101/00 C08L 101/00 (72)発明者 森田 好次 千葉県市原市千種海岸2番2 東レ・ダウ コーニング・シリコーン株式会社研究開発 本部内────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. 6 Identification symbol FI // C08L 101/00 C08L 101/00 (72) Inventor Yoshiji Morita 2-2 Chigusa Coast, Ichihara-shi, Chiba Dow Corning Toray Silicone Co., Ltd.
Claims (5)
たは式:−R1−NH−R1−NHR2(式中、R1は炭素
原子数1〜9の二価炭化水素基であり、R2は水素原子
または炭素原子数1〜6の一価炭化水素基である。)で
示されるアミノ基を有し、側鎖に炭素原子数4以上のア
ルケニル基を有するジオルガノポリシロキサンを主剤と
する有機樹脂改質剤。 1. A compound represented by the formula: -R 1 -NHR 2 or a formula: -R 1 -NH-R 1 -NHR 2 wherein R 1 is a divalent carbon having 1 to 9 carbon atoms. R 2 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.) And a dialkyl group having an alkenyl group having 4 or more carbon atoms in a side chain. Organic resin modifier mainly composed of organopolysiloxane.
種の一価炭化水素基であり、Xは式:−R1−NHR2ま
たは式:−R1−NH−R1−NHR2で示されるアミノ
基(式中、R1は炭素原子数1〜9の二価炭化水素基で
あり、R2は水素原子または炭素原子数1〜6の一価炭
化水素基である。)であり、Yは炭素原子数4以上のア
ルケニル基であり、mは0〜1,000の整数であり、
nは1〜1,000の整数である。}で示される請求項
1記載の有機樹脂改質剤。2. The diorganopolysiloxane has the general formula: In the formula, R is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, and X is the formula: —R 1 —NHR 2 or the formula: —R 1 —NH—R 1 —NHR 2 Wherein R 1 is a divalent hydrocarbon group having 1 to 9 carbon atoms, and R 2 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. Y is an alkenyl group having 4 or more carbon atoms, m is an integer of 0 to 1,000,
n is an integer of 1 to 1,000. The organic resin modifier according to claim 1, which is represented by 改 質.
有機樹脂改質剤。3. The organic resin modifier according to claim 2, wherein Y is a hexenyl group.
質された有機樹脂。4. An organic resin modified by the organic resin modifier according to claim 1.
質されたポリイミド樹脂。5. A polyimide resin modified by the organic resin modifier according to claim 1.
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JP17655897A JP3974686B2 (en) | 1997-06-17 | 1997-06-17 | Organic resin modifier and organic resin |
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JP17655897A JP3974686B2 (en) | 1997-06-17 | 1997-06-17 | Organic resin modifier and organic resin |
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JP3974686B2 JP3974686B2 (en) | 2007-09-12 |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000319386A (en) * | 1999-04-30 | 2000-11-21 | Dow Corning Toray Silicone Co Ltd | Silicone-containing polyimide resin, silicone-containing polyamic acid and their production |
JP2001206949A (en) * | 2000-01-28 | 2001-07-31 | Dow Corning Toray Silicone Co Ltd | Method of producing cyclic siloxane |
JP2009062429A (en) * | 2007-09-05 | 2009-03-26 | Shin Etsu Chem Co Ltd | Thermosetting polyimide silicone resin composition |
WO2012053548A1 (en) * | 2010-10-19 | 2012-04-26 | 旭硝子株式会社 | Resin composition, laminate and process for production thereof, structure and process for production thereof, and process for production of electronic device |
JP2015063622A (en) * | 2013-09-25 | 2015-04-09 | Jnc株式会社 | Cured film-forming composition |
-
1997
- 1997-06-17 JP JP17655897A patent/JP3974686B2/en not_active Expired - Fee Related
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000319386A (en) * | 1999-04-30 | 2000-11-21 | Dow Corning Toray Silicone Co Ltd | Silicone-containing polyimide resin, silicone-containing polyamic acid and their production |
JP4509247B2 (en) * | 1999-04-30 | 2010-07-21 | 東レ・ダウコーニング株式会社 | Silicone-containing polyimide resin, silicone-containing polyamic acid and method for producing them |
JP2001206949A (en) * | 2000-01-28 | 2001-07-31 | Dow Corning Toray Silicone Co Ltd | Method of producing cyclic siloxane |
JP2009062429A (en) * | 2007-09-05 | 2009-03-26 | Shin Etsu Chem Co Ltd | Thermosetting polyimide silicone resin composition |
JP4590443B2 (en) * | 2007-09-05 | 2010-12-01 | 信越化学工業株式会社 | Thermosetting polyimide silicone resin composition |
WO2012053548A1 (en) * | 2010-10-19 | 2012-04-26 | 旭硝子株式会社 | Resin composition, laminate and process for production thereof, structure and process for production thereof, and process for production of electronic device |
JPWO2012053548A1 (en) * | 2010-10-19 | 2014-02-24 | 旭硝子株式会社 | RESIN COMPOSITION, LAMINATE, ITS MANUFACTURING METHOD, STRUCTURE, ITS MANUFACTURING METHOD, AND ELECTRONIC DEVICE MANUFACTURING METHOD |
JP2015063622A (en) * | 2013-09-25 | 2015-04-09 | Jnc株式会社 | Cured film-forming composition |
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