JPH07304950A - Polyimidesiloxane composition - Google Patents
Polyimidesiloxane compositionInfo
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- JPH07304950A JPH07304950A JP5904595A JP5904595A JPH07304950A JP H07304950 A JPH07304950 A JP H07304950A JP 5904595 A JP5904595 A JP 5904595A JP 5904595 A JP5904595 A JP 5904595A JP H07304950 A JPH07304950 A JP H07304950A
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、可溶性のポリイミド
シロキサン、エポキシ樹脂、及びタルクを含有してなる
ポリイミドシロキサンの溶液組成物に係わるもので、そ
の組成物は、耐熱性、密着性、耐薬品性（特に耐ハンダ
フラックス性、耐スズメッキ液性）及び貯蔵安定性に優
れ、フレキシブル配線板上にスクリーン印刷などで保護
膜の形成が可能である印刷用インキ、塗布用ワニスなど
の用途に好適に使用される。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solution composition of polyimide siloxane containing soluble polyimide siloxane, epoxy resin and talc, the composition having heat resistance, adhesion and chemical resistance. It has excellent properties (especially solder flux resistance, tin plating resistance) and storage stability, and is suitable for applications such as printing ink and coating varnish that can form a protective film by screen printing on flexible wiring boards. used.
【０００２】この発明のポリイミドシロキサンの組成物
は、その溶液組成物をシリコンウエハー、フレキシブル
配線基板などに塗布し、乾燥・硬化して保護膜を形成し
た場合に、実質的にカールを引き起こすことがなく、又
その保護膜が優れた耐屈曲性、耐半田性（耐熱性）を有
すると共に、基板への密着性を有し、シランカップリン
グ剤などの密着促進剤で予め基板の前処理をする必要が
ないので、例えば、ＩＣ，ＬＳＩのパッシベーション膜
や、ダイオードのジャンクションコートなどの用途に、
上記前処理を行うことなく優れた保護膜を形成させるこ
とができる。The composition of the polyimidesiloxane of the present invention may cause curling substantially when the solution composition is applied to a silicon wafer, a flexible wiring board or the like and dried and cured to form a protective film. In addition, the protective film has excellent bending resistance, solder resistance (heat resistance), and has adhesion to the substrate, and the substrate is pretreated with an adhesion promoter such as a silane coupling agent. Since it is not necessary, for example, for applications such as IC and LSI passivation films and diode junction coats,
An excellent protective film can be formed without performing the above pretreatment.
【０００３】[0003]
【従来の技術】従来、芳香族ポリイミド、エポキシ樹脂
などを電気絶縁性の保護膜として利用することは、例え
ば、固体素子への絶縁膜、パッシベーション膜、半導体
集積回路、フレキシブル配線板などの絶縁膜などの用途
において知られている。一般に、エポキシ樹脂は硬化剤
の併用が必要であり、その硬化剤に係わる保存安定性、
二液調製のための作業性などの種々の問題があったり、
又、前述の絶縁膜として使用した場合に、熱硬化によっ
て形成される絶縁膜が剛直であり、柔軟性に欠け、屈曲
性に劣るという問題があった。2. Description of the Related Art Conventionally, the use of aromatic polyimide, epoxy resin, or the like as an electrically insulating protective film is known as, for example, an insulating film for a solid element, a passivation film, a semiconductor integrated circuit, an insulating film for a flexible wiring board, or the like. It is known for such uses. Generally, an epoxy resin needs to be used in combination with a curing agent, and the storage stability of the curing agent,
There are various problems such as workability for two-component preparation,
Further, when used as the above-mentioned insulating film, there is a problem that the insulating film formed by thermosetting is rigid, lacks flexibility and is inferior in flexibility.
【０００４】又、一般に芳香族ポリイミドは、有機溶媒
に溶解し難いために、芳香族ポリイミドの前駆体（芳香
族ポリアミック酸）の溶液として使用して、塗布膜を形
成し、次いで乾燥とイミド化とを高温で長時間、加熱処
理することによって、芳香族ポリイミドの保護膜を形成
する必要があり、保護すべき電気又は電子部材自体が熱
劣化するという問題があった。Further, since aromatic polyimide is generally difficult to dissolve in an organic solvent, it is used as a solution of a precursor of aromatic polyimide (aromatic polyamic acid) to form a coating film, followed by drying and imidization. It is necessary to form a protective film of aromatic polyimide by heat-treating at high temperature for a long time, and there is a problem that the electrical or electronic member itself to be protected is thermally deteriorated.
【０００５】一方、有機溶剤に可溶性の芳香族ポリイミ
ドは、例えば、特公昭５７−４１４９１号公報に記載さ
れているようなビフェニルテトラカルボン酸とジアミン
化合物とを有機極性溶媒中で重合及びイミド化した芳香
族ポリイミドが知られているが、そのポリイミドは、シ
リコンウェハー、ガラス板、フレキシブル基板などの基
板との密着性（接着性）が充分なかったので予め基板な
どを密着促進剤で処理しておくなどの方法が必要であっ
た。On the other hand, an aromatic polyimide soluble in an organic solvent is obtained by polymerizing and imidizing a biphenyltetracarboxylic acid and a diamine compound as described in JP-B-57-41491 in an organic polar solvent. Aromatic polyimide is known, but the polyimide does not have sufficient adhesiveness (adhesiveness) with substrates such as silicon wafers, glass plates, and flexible substrates, so the substrate is treated with an adhesion promoter in advance. I needed a method such as.
【０００６】[0006]
【発明が解決しようとする課題】この発明の目的は、有
機溶剤に対して高い溶解性を有し、保護膜を形成した場
合に、高い耐熱性、非カール性、密着性を同時に有して
いて、しかも、エポキシ樹脂との相溶性がよく、接着剤
などに悪影響を及ぼさないものであって、充分な耐熱
性、耐薬品性（特に耐ハンダフラックス性、耐スズメッ
キ液性）、耐屈曲性を有する保護膜などを容易に形成す
ることができるポリイミドシロキサンの組成物（溶液組
成物）を提供することである。The object of the present invention is to have a high solubility in an organic solvent and, at the same time, have a high heat resistance, a non-curl property and an adhesive property when a protective film is formed. In addition, it has good compatibility with epoxy resin and does not adversely affect adhesives, and has sufficient heat resistance, chemical resistance (especially solder flux resistance, tin plating solution resistance), and bending resistance. A polyimide siloxane composition (solution composition) capable of easily forming a protective film or the like having
【０００７】この発明者らは、可溶性のポリイミドシロ
キサン、エポキシ樹脂、及びタルクからなるポリイミド
シロキサンの組成物を使用すると、上述の目的を達成で
きることを知り、この発明に至った。The present inventors have found that the above object can be achieved by using a composition of a polyimide siloxane composed of a soluble polyimide siloxane, an epoxy resin, and talc, and arrived at the present invention.
【０００８】[0008]
【課題を解決するための手段】この発明は、（ａ）一般
式（１）The present invention provides (a) general formula (1)
【０００９】[0009]
【化１３】 [Chemical 13]
【００１０】一般式（２）General formula (2)
【００１１】[0011]
【化１４】 及び、一般式（３）[Chemical 14] And the general formula (3)
【００１２】[0012]
【化１５】 [Chemical 15]
【００１３】（ただし、式中のＲ１は芳香族テトラカル
ボン酸からテトラカルボン酸を除く４価の残基を示し、
Ｒ２は一般式（４）のジアミノポリシロキサンのアミノ
基を除く２価の残基を示し、Ｒ３は一般式（５）で示さ
れる芳香族ジアミン化合物よりアミノ基を除く２価の残
基を示し、Ｒ４は一般式（４）及び一般式（５）で示さ
れるジアミン化合物を除くジアミン化合物からアミノ基
を除く２価の残基を示し、ｎ１は３〜３０の整数を示
し、Ｒ５は２価の炭化水素基又はフェニル基を示し、Ｒ
６は独立に炭素数１〜３のアルキル基またはフェニル基
を示し、×は直接結合又は一般式（６）で示し、ｒ１は
水酸基又はカルボキシル基を示し、ｎ２は１又は２の整
数を示し、ｎ３は０〜３の整数を示し、Ｒ７、Ｒ８は水
素、メチル基又はハロゲン化メチル基を示し、ｍ１、ｍ
２及びｍ３の割合が各成分合計１００モル％中ｍ１が４
５〜８０モル％、ｍ２が０．５〜４０モル％及びｍ３が
残部である。） 一般式（４）(In the formula, R1 represents a tetravalent residue obtained by removing tetracarboxylic acid from aromatic tetracarboxylic acid,
R2 represents a divalent residue excluding an amino group of the diaminopolysiloxane of the general formula (4), and R3 represents a divalent residue excluding an amino group from the aromatic diamine compound represented by the general formula (5). , R4 represents a divalent residue excluding an amino group from a diamine compound other than the diamine compounds represented by the general formulas (4) and (5), n1 represents an integer of 3 to 30, and R5 represents a divalent compound. Represents a hydrocarbon group or a phenyl group of R,
6 independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, x represents a direct bond or is represented by the general formula (6), r1 represents a hydroxyl group or a carboxyl group, n2 represents an integer of 1 or 2, n3 represents an integer of 0 to 3, R7 and R8 represent hydrogen, a methyl group or a halogenated methyl group, and m1 and m
The ratio of 2 and m3 is 100% by mol of each component, and m1 is 4
5 to 80 mol%, m2 is 0.5 to 40 mol%, and m3 is the balance. ) General formula (4)
【００１４】[0014]
【化１６】 一般式（５）[Chemical 16] General formula (5)
【００１５】[0015]
【化１７】 一般式（６）[Chemical 17] General formula (6)
【００１６】[0016]
【化１８】 [Chemical 18]
【００１７】で示される有機溶剤可溶性のポリイミドシ
ロキサン１００重量部、（ｂ）エポキシ樹脂１〜５０重
量部、（ｃ）２〜１５０重量部のその粒子が偏平状で平
均粒子径が１〜３μm のタルクからなることを特徴とす
るポリイミドシロキサンの組成物に関する。100 parts by weight of an organic solvent-soluble polyimide siloxane, (b) 1 to 50 parts by weight of epoxy resin, and (c) 2 to 150 parts by weight of the particles are flat and have an average particle diameter of 1 to 3 μm. It relates to a composition of a polyimide siloxane, which is composed of talc.
【００１８】また、この発明は、（ａ）一般式（１）The present invention also provides (a) the general formula (1).
【００１９】[0019]
【化１９】 [Chemical 19]
【００２０】一般式（２）General formula (2)
【００２１】[0021]
【化２０】 及び、一般式（３）[Chemical 20] And the general formula (3)
【００２２】[0022]
【化２１】 [Chemical 21]
【００２３】（ただし、式中のＲ１は芳香族テトラカル
ボン酸からテトラカルボン酸を除く４価の残基を示し、
Ｒ２は一般式（４）のジアミノポリシロキサンのアミノ
基を除く２価の残基を示し、Ｒ３は一般式（５）で示さ
れる芳香族ジアミン化合物よりアミノ基を除く２価の残
基を示し、Ｒ４は一般式（４）及び一般式（５）で示さ
れるジアミン化合物を除くジアミン化合物からアミノ基
を除く２価の残基を示し、ｎ１は３〜３０の整数を示
し、Ｒ５は２価の炭化水素基又はフェニル基を示し、Ｒ
６は独立に炭素数１〜３のアルキル基またはフェニル基
を示し、×は直接結合又は一般式（６）で示し、ｒ１は
水酸基又はカルボキシル基を示し、ｎ２は１又は２の整
数を示し、ｎ３は０〜３の整数を示し、Ｒ７、Ｒ８は水
素、メチル基又はハロゲン化メチル基を示し、ｍ１、ｍ
２及びｍ３の割合が各成分合計１００モル％中ｍ１が４
５〜８０モル％、ｍ２が０．５〜４０モル％及びｍ３が
残部である。） 一般式（４）(In the formula, R1 represents a tetravalent residue obtained by removing tetracarboxylic acid from aromatic tetracarboxylic acid,
R2 represents a divalent residue excluding an amino group of the diaminopolysiloxane of the general formula (4), and R3 represents a divalent residue excluding an amino group from the aromatic diamine compound represented by the general formula (5). , R4 represents a divalent residue excluding an amino group from a diamine compound other than the diamine compounds represented by the general formulas (4) and (5), n1 represents an integer of 3 to 30, and R5 represents a divalent compound. Represents a hydrocarbon group or a phenyl group of R,
6 independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, x represents a direct bond or is represented by the general formula (6), r1 represents a hydroxyl group or a carboxyl group, n2 represents an integer of 1 or 2, n3 represents an integer of 0 to 3, R7 and R8 represent hydrogen, a methyl group or a halogenated methyl group, and m1 and m
The ratio of 2 and m3 is 100% by mol of each component, and m1 is 4
5 to 80 mol%, m2 is 0.5 to 40 mol%, and m3 is the balance. ) General formula (4)
【００２４】[0024]
【化２２】 一般式（５）[Chemical formula 22] General formula (5)
【００２５】[0025]
【化２３】 一般式（６）[Chemical formula 23] General formula (6)
【００２６】[0026]
【化２４】 [Chemical formula 24]
【００２７】で示される有機溶剤可溶性のポリイミドシ
ロキサン１００重量部、（ｂ）エポキシ樹脂１〜５０重
量部、（ｃ）２〜１５０重量部のその粒子が偏平状で平
均粒子径が１〜３μm のタルクを含有するポリイミドシ
ロキサンの組成物を加熱してなることを特徴とする硬化
物に関する。100 parts by weight of an organic solvent-soluble polyimide siloxane, (b) 1 to 50 parts by weight of an epoxy resin, and (c) 2 to 150 parts by weight of the particles are flat and have an average particle diameter of 1 to 3 μm. It relates to a cured product obtained by heating a polyimide siloxane composition containing talc.
【００２８】この発明において、芳香族テトラカルボン
酸としては、２、３、３’、４’−ビフェニルテトラカ
ルボン酸、３、３’、４、４’−ビフェニルテトラカル
ボン酸、３、３’、４、４’−ジフェニルエ−テルテト
ラカルボン酸、３、３’、４、４’−ジフェニルスルホ
ンテトラカルボン酸、３、３’、４、４’−ベンゾフェ
ノンテトラカルボン酸、２、２−ビス（３、４−ベンゼ
ンジカルボン酸無水物）ヘキサフルオロプロパン、ピロ
メリット酸、１、４−ビス（３、４−ベンゼンジカルボ
ン酸）ベンゼン、２、２−ビス〔４−（３、４−フェノ
キシジカルボン酸）フェニル〕プロパン、又はそれらの
無水物や低級アルコ−ルのエステル化物を、８０モル％
以上、特に８５〜１００モル％含有する芳香族テトラカ
ルボン酸が使用される。これらのなかでも特に、２、
３、３’、４’−ビフェニルテトラカルボン酸、３、
３’、４、４’−ジフェニルエ−テルテトラカルボン酸
が、前記ポリイミドシロキサンの有機溶媒に対する溶解
性が優れているので好適である。In the present invention, as the aromatic tetracarboxylic acid, 2,3,3 ', 4'-biphenyltetracarboxylic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 3,3 ', 4,4'-diphenylethertetracarboxylic acid, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 3,3', 4,4'-benzophenone tetracarboxylic acid, 2,2-bis ( 3,4-benzenedicarboxylic acid anhydride) hexafluoropropane, pyromellitic acid, 1,4-bis (3,4-benzenedicarboxylic acid) benzene, 2,2-bis [4- (3,4-phenoxydicarboxylic acid) ) Phenyl] propane, or their anhydrides or esterified products of lower alcohol, in an amount of 80 mol%
Above all, aromatic tetracarboxylic acid containing 85 to 100 mol% is particularly used. Among these, especially 2,
3,3 ', 4'-biphenyltetracarboxylic acid, 3,
3 ′, 4,4′-diphenylethertetracarboxylic acid is preferable because it has excellent solubility in the organic solvent of the polyimidesiloxane.
【００２９】この発明において、一般式（４）で示され
るジアミノポリシロキサンとしては、式中のＲ５は２価
の炭化水素基を示し炭素数が２〜６、好ましくは３〜５
の複数のメチレン基又はフェニレン基からなる。Ｒ６は
独立に炭素数１〜３のメチル基、エチル基、プロピル基
などのアルキル基又はフェニル基を示し、ｎは３〜３
０、好ましくは３〜２０を示す。ｎの数が小さいとカ−
ル性が高くなり好ましくなく、ｎの数があまり大きすぎ
たりすると耐薬品性が低くなったり、芳香族テトラカル
ボン酸成分との反応性が低下したり、得られるポリイミ
ドシロキサンの分子量が低くなったり、有機溶媒に対す
る溶解性が低くなったり、他の有機化合物との相溶性が
悪くなるので前記程度のものが適当である。In the present invention, as the diaminopolysiloxane represented by the general formula (4), R5 in the formula is a divalent hydrocarbon group and has 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms.
A plurality of methylene groups or phenylene groups. R6 independently represents an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group or a phenyl group, and n is 3 to 3
0, preferably 3 to 20 is shown. If the number of n is small
If the number of n is too large, the chemical resistance will decrease, the reactivity with the aromatic tetracarboxylic acid component will decrease, and the molecular weight of the resulting polyimidesiloxane will decrease. Since the solubility in an organic solvent becomes low and the compatibility with other organic compounds becomes poor, the above-mentioned degree is suitable.
【００３０】ジアミノポリシロキサンの具体的化合物の
例としてはα、ω−ビス（２−アミノエチル) ポリジメ
チルシロキサン、α、ω−ビス（３−アミノプロピル)
ポリジメチルシロキサン、α、ω−ビス（４−アミノフ
ェニル) ポリジメチルシロキサン、α、ω−ビス（４−
アミノ−３−メチルフェニル) ポリジメチルシロキサ
ン、α、ω−ビス（３−アミノプロピル) ポリジフェニ
ルシロキサン、α、ω−ビス（４−アミノブチル) ポリ
ジメチルシロキサンなどが挙げられる。Specific examples of the diaminopolysiloxane include α, ω-bis (2-aminoethyl) polydimethylsiloxane and α, ω-bis (3-aminopropyl).
Polydimethylsiloxane, α, ω-bis (4-aminophenyl) polydimethylsiloxane, α, ω-bis (4-
Amino-3-methylphenyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydiphenylsiloxane, α, ω-bis (4-aminobutyl) polydimethylsiloxane and the like can be mentioned.
【００３１】この発明において、一般式（５）で示され
るジアミン化合物としては、３、５−ジアミノ安息香
酸、２、４−ジアミノ安息香酸などのベンゼンカルボン
酸類、３、３’−ジアミノ、４、４’−ジハイドロキシ
ビフェニル、４、４’−ジアミノ、３、３’−ジハイド
ロキシビフェニル、４、４’−ジアミノ、２、２’−ジ
ハイドロキシビフェニル、４、４’−ジアミノ、２、
２’、５、５’−テトラハイドロキシビフェニルなどの
ヒドロキシビフェニル化合物類、３、３’−ジアミノ、
４、４’−ジカルボキシビフェニル、４、４’−ジアミ
ノ、３、３’−ジカルボキシビフェニル、４、４’−ジ
アミノ、２、２’−ジカルボキシビフェニル、４、４’
−ジアミノ、２、２’、５、５’−−テトラカルボキシ
ビフェニルなどのカルボキシビフェニル化合物類、３、
３’−ジアミノ、４、４’−ジハイドロキシジフェニル
メタン、４、４’−ジアミノ、３、３’−ジハイドロキ
シジフェニルメタン、４、４’−ジアミノ、２、２’−
ジハイドロキシジフェニルメタン、２、２−ビス〔３−
アミノ、４、−ハイドロキシフェニル〕プロパン、２、
２−ビス〔４−アミノ、３、−ハイドロキシフェニル〕
プロパン、２、２−ビス〔３−アミノ、４、−ハイドロ
キシフェニル〕ヘキサフルオロプロパン、４、４’−ジ
アミノ、２、２’、５、５’−テトラハイドロキシジフ
ェニルメタンなどのヒドロキシジフェニルアルカン化合
物類、３、３’−ジアミノ、４、４’−ジカルボキシジ
フェニルメタン、４、４’−ジアミノ、３、３’−ジカ
ルボキシジフェニルメタン、４、４’−ジアミノ、２、
２’−ジカルボキシジフェニルメタン、２、２−ビス
〔３−アミノ、４、−カルボキシフェニル〕プロパン、
２、２−ビス〔４−アミノ、３、−カルボキシフェニ
ル〕プロパン、２、２−ビス〔３−アミノ、４、−カル
ボキシフェニル〕ヘキサフルオロプロパン、４、４’−
ジアミノ、２、２’、５、５’−テトラカルボキシビフ
ェニルなどのカルボキシジフェニルアルカン化合物類、
３、３’−ジアミノ、４、４’−ジハイドロキシジフェ
ニルエ−テル、４、４’−ジアミノ、３、３’−ジハイ
ドロキシジフェニルエ−テル、４、４’−ジアミノ、
２、２’−ジハイドロキシジフェニルエ−テル、４、
４’−ジアミノ、２、２’、５、５’−テトラハイドロ
キシジフェニルエ−テルなどのヒドロキシジフェニルエ
−テル化合物類、３、３’−ジアミノ、４、４’−ジカ
ルボキシジフェニルエ−テル、４、４’−ジアミノ、
３、３’−ジカルボキシジフェニルエ−テル、４、４’
−ジアミノ、２、２’−ジカルボキシジフェニルエ−テ
ル、４、４’−ジアミノ、２、２’、５、５’−テトラ
カルボキシジフェニルエ−テルなどのカルボキシジフェ
ニルエ−テル化合物類、３、３’−ジアミノ、４、４’
−ジハイドロキシジフェニルスルホン、４、４’−ジア
ミノ、３、３’−ジハイドロキシジフェニルスルホン、
４、４’−ジアミノ、２、２’−ジハイドロキシジフェ
ニルスルホン、４、４’−ジアミノ、２、２’、５、
５’−テトラハイドロキシジフェニルスルホンなどのヒ
ドロキシジフェニルスルホン化合物類、３、３’−ジア
ミノ、４、４’−ジカルボキシジフェニルスルホン、
４、４’−ジアミノ、３、３’−ジカルボキシジフェニ
ルスルホン、４、４’−ジアミノ、２、２’−ジカルボ
キシジフェニルスルホン、４、４’−ジアミノ、２、
２’、５、５’−テトラカルボキシジフェニルスルホン
などのカルボキシジフェニルスルホン化合物類、２、２
−ビス〔４−（４−アミノ、３−ハイドロキシフェノキ
シ）フェニル〕プロパンなどのビス（ハイドロキシフェ
ニキシフェニル）アルカン化合物類、２、２−ビス〔４
−（４−アミノ、３−カルボキシフェノキシ）フェニ
ル〕プロパンなどのビス（カルボキシフェノキシフェニ
ル）アルカン化合物類、４、４’−ビス（４−アミノ、
３−ハイドロキシフェノキシ）ビフェニルなどのビス
（ハイドロキシフェノキシ）ビフェニル化合物類、４、
４’−ビス（４−アミノ、３−カルボキシフェノキシ）
ビフェニルなどのビス（カルボキシフェノキシ）ビフェ
ニル化合物類、２、２−ビス〔４−（４−アミノ、３−
ハイドロキシフェノキシ）フェニル〕スルホンなどのビ
ス（ハイドロキシフェニキシフェニル）スルホン化合物
類、２、２−ビス〔４−（４−アミノ、３−カルボキシ
フェノキシ）フェニル〕スルホンなどのビス（カルボキ
シフェノキシフェニル）スルホン化合物類などを挙げる
ことができる。In the present invention, examples of the diamine compound represented by the general formula (5) include benzenecarboxylic acids such as 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, 3,3′-diamino and 4, 4'-dihydroxybiphenyl, 4,4'-diamino, 3,3'-dihydroxybiphenyl, 4,4'-diamino, 2,2'-dihydroxybiphenyl, 4,4'-diamino, 2,
Hydroxybiphenyl compounds such as 2 ′, 5,5′-tetrahydroxybiphenyl, 3,3′-diamino,
4,4'-dicarboxybiphenyl, 4,4'-diamino, 3,3'-dicarboxybiphenyl, 4,4'-diamino, 2,2'-dicarboxybiphenyl, 4,4 '
-Diamino, 2,2 ', 5,5'-carboxybiphenyl compounds such as tetracarboxybiphenyl, 3,
3'-diamino, 4,4'-dihydroxydiphenylmethane, 4,4'-diamino, 3,3'-dihydroxydiphenylmethane, 4,4'-diamino, 2,2'-
Dihydroxydiphenylmethane, 2,2-bis [3-
Amino, 4, -hydroxyphenyl] propane, 2,
2-bis [4-amino, 3, -hydroxyphenyl]
Propane, 2,2-bis [3-amino, 4, -hydroxyphenyl] hexafluoropropane, 4,4'-diamino, hydroxydiphenylalkane compounds such as 2,2 ', 5,5'-tetrahydroxydiphenylmethane, 3,3'-diamino, 4,4'-dicarboxydiphenylmethane, 4,4'-diamino, 3,3'-dicarboxydiphenylmethane, 4,4'-diamino, 2,
2'-dicarboxydiphenylmethane, 2,2-bis [3-amino, 4, -carboxyphenyl] propane,
2,2-bis [4-amino, 3, -carboxyphenyl] propane, 2,2-bis [3-amino, 4, -carboxyphenyl] hexafluoropropane, 4,4'-
Carboxydiphenylalkane compounds such as diamino, 2,2 ′, 5,5′-tetracarboxybiphenyl,
3,3'-diamino, 4,4'-dihydroxydiphenyl ether, 4,4'-diamino, 3,3'-dihydroxydiphenyl ether, 4,4'-diamino,
2,2'-dihydroxydiphenyl ether, 4,
Hydroxydiphenyl ether compounds such as 4'-diamino, 2,2 ', 5,5'-tetrahydroxydiphenyl ether, 3,3'-diamino, 4,4'-dicarboxydiphenyl ether, 4,4'-diamino,
3,3'-dicarboxydiphenyl ether, 4,4 '
-Diamino, 2,2'-dicarboxydiphenyl ether, carboxydiphenyl ether compounds such as 4,4'-diamino, 2,2 ', 5,5'-tetracarboxydiphenyl ether, 3, 3'-diamino, 4, 4 '
-Dihydroxydiphenyl sulfone, 4,4'-diamino, 3,3'-dihydroxydiphenyl sulfone,
4,4'-diamino, 2,2'-dihydroxydiphenyl sulfone, 4,4'-diamino, 2,2 ', 5,
Hydroxydiphenyl sulfone compounds such as 5′-tetrahydroxydiphenyl sulfone, 3,3′-diamino, 4,4′-dicarboxydiphenyl sulfone,
4,4'-diamino, 3,3'-dicarboxydiphenyl sulfone, 4,4'-diamino, 2,2'-dicarboxydiphenyl sulfone, 4,4'-diamino, 2,
Carboxydiphenyl sulfone compounds such as 2 ′, 5,5′-tetracarboxydiphenyl sulfone, 2,2
-Bis (hydroxyphenoxyphenyl) alkane compounds such as bis [4- (4-amino, 3-hydroxyphenoxy) phenyl] propane, 2,2-bis [4
Bis (carboxyphenoxyphenyl) alkane compounds such as-(4-amino, 3-carboxyphenoxy) phenyl] propane, 4,4'-bis (4-amino,
Bis (hydroxyphenoxy) biphenyl compounds such as 3-hydroxyphenoxy) biphenyl, 4,
4'-bis (4-amino, 3-carboxyphenoxy)
Bis (carboxyphenoxy) biphenyl compounds such as biphenyl, 2,2-bis [4- (4-amino, 3-
Bis (hydroxyphenoxyphenyl) sulfone compounds such as hydroxyphenoxy) phenyl] sulfone and bis (carboxyphenoxyphenyl) sulfone compounds such as 2,2-bis [4- (4-amino, 3-carboxyphenoxy) phenyl] sulfone Kind of things can be mentioned.
【００３２】この発明において一般式（３）に示される
Ｒ４は一般式（４）及び一般式（５）で示されるジアミ
ン化合物を除くジアミン化合物よりアミノ基を除いた２
価の残基を示し、１、４−ジアミノベンゼン、１、３−
ジアミノベンゼン、２、４−ジアミノトルエン、１、４
−ジアミノ、２、５−ジハロゲノベンゼンなどのベンゼ
ン１個を含むジアミン類、ビス（４−アミノフェニル）
エ−テル、ビス（３−アミノフェニル）エ−テル、ビス
（４−アミノフェニル）スルホン、ビス（３−アミノフ
ェニル）スルホン、ビス（４−アミノフェニル）メタ
ン、ビス（３−アミノフェニル）メタン、ビス（４−ア
ミノフェニル）スルフィド、ビス（３−アミノフェニ
ル）スルフィド、２、２−ビス（４−アミノフェニル）
プロパン、２、２−ビス（３−アミノフェニル）プロパ
ン、２、２−ビス（４−アミノフェニル）ヘキサフルオ
ロプロパン、ｏ−ジアニシジン、ｏ−トリジン、トリジ
ンスルホン酸類などのベンゼン２個を含むジアミン類、
１、４−ビス（４−アミノフェノキシ）ベンゼン、１、
４−ビス（３−アミノフェノキシ）ベンゼン、１、４−
ビス（４−アミノフェニル）ベンゼン、１、４−ビス
（３−アミノフェニル）ベンゼン、α、α’−ビス（４
−アミノフェニル）−１、４−ジイソプロピルベンゼ
ン、α、α’−ビス（４−アミノフェニル）−１、３−
ジイソプロピルベンゼンなどのベンゼン３個を含むジア
ミン類２、２−ビス〔４−（４−アミノフェノキシ）フ
ェニル〕プロパン２、２−ビス〔４−（４−アミノフェ
ノキシ）フェニル〕ヘキサフルオロプロパン２、２−ビ
ス〔４−（４−アミノフェノキシ）フェニル〕スルホン
４、４’−（４−アミノフェノキシ）ビフェニル、９、
９−ビス（４−アミノフェニル）フルオレン５、１０−
ビス（４−アミノフェニル）アントラセンなどのベンゼ
ン４個以上を含むジアミン類などのジアミン化合物が挙
げられる。ヘキサメチレンジアミン、ジアミノドデカン
など脂肪族ジアミン化合物を上記ジアミンと共に使用す
ることができる。In the present invention, R4 represented by the general formula (3) is a diamine compound excluding the diamine compounds represented by the general formulas (4) and (5) from which an amino group is removed.
Indicates a valent residue, 1,4-diaminobenzene, 1,3-
Diaminobenzene, 2,4-diaminotoluene, 1,4
-Diamino, diamine containing one benzene such as 2,5-dihalogenobenzene, bis (4-aminophenyl)
Ether, bis (3-aminophenyl) ether, bis (4-aminophenyl) sulfone, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) methane, bis (3-aminophenyl) methane , Bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfide, 2,2-bis (4-aminophenyl)
Diamines containing two benzenes such as propane, 2,2-bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, o-dianisidine, o-tolidine, and tolidinesulfonic acids. ,
1,4-bis (4-aminophenoxy) benzene, 1,
4-bis (3-aminophenoxy) benzene, 1,4-
Bis (4-aminophenyl) benzene, 1,4-bis (3-aminophenyl) benzene, α, α′-bis (4
-Aminophenyl) -1,4-diisopropylbenzene, α, α'-bis (4-aminophenyl) -1,3-
Diamines containing 3 benzenes such as diisopropylbenzene 2,2-bis [4- (4-aminophenoxy) phenyl] propane 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane 2,2 -Bis [4- (4-aminophenoxy) phenyl] sulfone 4,4 '-(4-aminophenoxy) biphenyl, 9,
9-bis (4-aminophenyl) fluorene 5,10-
Examples include diamine compounds such as diamines containing four or more benzenes such as bis (4-aminophenyl) anthracene. Aliphatic diamine compounds such as hexamethylenediamine and diaminododecane can be used with the above diamines.
【００３３】この発明において、ポリイミドシロキサン
成分中の一般式（１）、一般式（２）と一般式（３）の
ユニットの割合は、それぞれ４５〜８０モル％、０．５
〜４０モル％及び残部、好ましくはそれぞれ４５〜７５
モル％、１〜４０モル％、０〜５０モル％、更に好まし
くはそれぞれ５０〜７５モル％、５〜３５モル％、５〜
４５モル％の割合で使用される。いずれかの成分が多す
ぎたり、少なすぎたりしてこれらの範囲をはずれると得
られるポリイミドシロキサンの有機溶媒に対する溶解性
が低下したり、他の有機化合物との相溶性が悪くなった
り、フレキシブル配線基板上に保護膜を形成する際に大
きくカールするようになったり、耐熱性が低下したり、
弾性率が高くなるので適当でない。In the present invention, the proportions of the units of the general formula (1), the general formula (2) and the general formula (3) in the polyimidesiloxane component are 45 to 80 mol% and 0.5, respectively.
-40 mol% and the balance, preferably 45-75, respectively
Mol%, 1-40 mol%, 0-50 mol%, more preferably 50-75 mol%, 5-35 mol%, 5-
Used in a proportion of 45 mol%. If either component is too much or too little and is out of these ranges, the solubility of the resulting polyimide siloxane in an organic solvent will be reduced, the compatibility with other organic compounds will be poor, and flexible wiring When the protective film is formed on the substrate, the curl becomes large, the heat resistance decreases,
Not suitable because of high elastic modulus.
【００３４】この発明において、ポリイミドシロキサン
は、次の方法で得られる。 (1) 芳香族テトラカルボン酸成分とジアミノポリシロキ
サン及び芳香族ジアミンのジアミン成分とを、略等モル
使用し、有機極性溶媒中で連続的に１５〜２５０℃で重
合及びイミド化させてポリイミドシロキサンを得る方
法。In the present invention, the polyimidesiloxane is obtained by the following method. (1) Polyimide siloxane obtained by continuously polymerizing and imidizing an aromatic tetracarboxylic acid component and a diamino polysiloxane and a diamine component of an aromatic diamine in an organic polar solvent at 15 to 250 ° C. in substantially equimolar amounts. How to get.
【００３５】(2) ジアミン成分を分けて、まず芳香族テ
トラカルボン酸成分の過剰量とジアミノポリシロキサン
とを有機極性溶媒中で１５〜２５０℃で重合、イミド化
させて、平均重合度１〜１０程度の末端に酸又は酸無水
物基を有するイミドシロキサンオリゴマーを調製し、別
に芳香族テトラカルボン酸成分と過剰量の芳香族ジアミ
ンとを有機極性溶媒中で１５〜２５０℃で重合、イミド
化させて、平均重合度１〜１０程度の末端にアミノ基を
有するイミドオリゴマーを調製し、次いでこの両者を、
酸成分とジアミン成分とが略等モルになるように混合し
て１５〜６０℃で反応させて、さらに１３０〜２５０℃
に昇温してブロックタイプのポリイミドシロキサンを得
る方法。(2) Dividing the diamine component, first, an excess amount of the aromatic tetracarboxylic acid component and diaminopolysiloxane are polymerized and imidized in an organic polar solvent at 15 to 250 ° C. to obtain an average degree of polymerization of 1 to 1. An imide siloxane oligomer having an acid or acid anhydride group at about 10 terminals is prepared, and an aromatic tetracarboxylic acid component and an excess amount of an aromatic diamine are separately polymerized and imidized in an organic polar solvent at 15 to 250 ° C. Then, an imide oligomer having an amino group at the terminal and having an average degree of polymerization of about 1 to 10 is prepared.
The acid component and the diamine component are mixed so as to be approximately equimolar and reacted at 15 to 60 ° C, and further 130 to 250 ° C.
A method of obtaining a block-type polyimide siloxane by elevating the temperature.
【００３６】(3) 芳香族テトラカルボン酸成分とジアミ
ノポリシロキサン及び芳香族ジアミンのジアミン成分と
を、略等モル使用し、有機極性溶媒中でまず２０〜８０
℃で重合させて一度ポリアミック酸を得た後に、イミド
化してポリイミドシロキサンを得る方法などがある。(3) The aromatic tetracarboxylic acid component and the diaminopolysiloxane and the diamine component of the aromatic diamine are used in approximately equimolar amounts, and they are first mixed in an organic polar solvent at 20-80.
There is a method in which the polyamic acid is once obtained by polymerization at ° C and then imidized to obtain a polyimidesiloxane.
【００３７】上記ポリイミドシロキサンを得る際に使用
される有機極性溶媒としては、アミド系溶媒、例えばN,
N-ジメチルアセトアミド、N,N-ジエチルアセトアミド、
N,N-ジメチルホルムアミド、N,N-ジエチルホルムアミ
ド、N-メチル-2- ピロリドンなど，硫黄原子を含有する
溶媒、例えばジメチルスルホキシド、ジエチルスルホキ
シド、ジメチルスルホン、ジエチルスルホン、ヘキサメ
チルスルホルアミドなど，フェノール系溶媒、例えばク
レゾール、フェノール、キシレノールなど，ジグライム
系溶媒例えばジエチレングリコール ジメチルエーテル
（ジグライム）、トリエチレングリコール ジメチルエ
ーテル（トリグライム）、テトラグライムなど、酸素原
子を分子内に有する溶媒、例えばアセトン、メタノー
ル、エタノール、エチレングリコール、ジオキサン、テ
トラヒドロフランなど，その他ピリジン、テトラメチル
尿素などを挙げることができる。また必要に応じてベン
ゼン、トルエン、キシレンなどの芳香族炭化水素系溶媒
やソルベントナフサ、ベンゾニトリルなど他の有機溶媒
を併用してもよい。The organic polar solvent used for obtaining the polyimidesiloxane is an amide solvent such as N,
N-dimethylacetamide, N, N-diethylacetamide,
N, N-dimethylformamide, N, N-diethylformamide, N-methyl-2-pyrrolidone, etc., a solvent containing a sulfur atom, such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, hexamethyl sulfolamide, Phenol-based solvents such as cresol, phenol, xylenol, etc., diglyme-based solvents such as diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraglyme, etc., solvents having an oxygen atom in the molecule, such as acetone, methanol, ethanol, Examples thereof include ethylene glycol, dioxane, tetrahydrofuran, etc., pyridine, tetramethylurea, etc. If necessary, an aromatic hydrocarbon solvent such as benzene, toluene or xylene, or another organic solvent such as solvent naphtha or benzonitrile may be used in combination.
【００３８】この発明において、ポリイミドシロキサン
は、前記(1) 〜(3) などいずれの方法で得られたものを
使用してもよいが、できるだけ高分子量で、イミド化率
が高く、有機極性溶媒に少なくとも３重量％以上、好ま
しくは５〜６０重量％、特に５〜５０％程度の高濃度で
溶解させることができるもので、２５℃の溶液粘度（Ｅ
型回転粘度計）が０．０１〜１０，０００ポイズ、特に
０．１〜１，０００ポイズであることが好ましい。In the present invention, the polyimide siloxane may be obtained by any method such as the above (1) to (3), but it has a high molecular weight as much as possible, a high imidization ratio, and an organic polar solvent. It can be dissolved at a high concentration of at least 3% by weight, preferably 5 to 60% by weight, and particularly about 5 to 50%, and has a solution viscosity (E
It is preferable that the mold rotational viscometer) is 0.01 to 10,000 poise, and particularly 0.1 to 1,000 poise.
【００３９】ポリイミドシロキサンのイミド化率は、９
０％以上、特には９５％以上が好ましく、分子量の目安
としての対数粘度（測定濃度：０．５g ／１００ミリリ
ットル、溶媒：N-メチル-2- ピロリドン、測定温度：３
０℃）が、０．０５〜３、好ましくは０．１〜２である
ものがよい。The imidization ratio of polyimidesiloxane is 9
0% or more, particularly 95% or more is preferable, and the logarithmic viscosity as a standard of molecular weight (measurement concentration: 0.5 g / 100 ml, solvent: N-methyl-2-pyrrolidone, measurement temperature: 3
(0 ° C.) is 0.05 to 3, preferably 0.1 to 2.
【００４０】この発明において使用するエポキシ樹脂と
しては、エポキシ当量が１００〜１０００程度であっ
て、分子量が４００〜５０００程度である液状又は固体
状のエポキシ樹脂が好ましい。例えば、ビスフェノール
Ａ型やビスフェノールＦ型のエポキシ樹脂（油化シェル
製：エピコート８０６、エピコート８２５など）、３官
能以上のエポキシ樹脂（油化シェル製：エピコート１５
２、エピコート１５４、エピコート１８０シリ−ズ、エ
ピコートエピコート１５７シリ−ズ、エピコート１０３
２シリ−ズ、チバガイギ−製：ＭＴ０１６３など）など
を挙げることができる。The epoxy resin used in the present invention is preferably a liquid or solid epoxy resin having an epoxy equivalent of about 100 to 1000 and a molecular weight of about 400 to 5000. For example, bisphenol A type or bisphenol F type epoxy resin (Okaka Shell: Epicoat 806, Epicoat 825, etc.), trifunctional or higher functional epoxy resin (Okaka Shell: Epicoat 15
2, Epikote 154, Epikote 180 series, Epikote Epikote 157 series, Epikote 103
2 series, manufactured by Ciba-Geigy: MT0163 and the like).
【００４１】この発明において、エポキシ樹脂の使用量
は、ポリイミドシロキサン１００重量部に対して、１〜
５０重量部、好ましくは５〜４０重量部である。使用量
が、余り多すぎたり、少なすぎると組成物がゲル化した
り、硬化後に耐熱性、耐薬品性が悪くなるので上記範囲
が好ましい。In the present invention, the amount of epoxy resin used is 1 to 100 parts by weight of polyimide siloxane.
It is 50 parts by weight, preferably 5 to 40 parts by weight. If the amount used is too large or too small, the composition will gel and the heat resistance and chemical resistance after curing will deteriorate, so the above range is preferred.
【００４２】エポキシ樹脂と共にヒドラジド類、イミダ
ゾ−ル類などのエポキシ樹脂の硬化を促進する添加成分
を使用してもよい。An additive component that accelerates the curing of the epoxy resin such as hydrazides and imidazoles may be used together with the epoxy resin.
【００４３】この発明において使用するタルクとして
は、その粒子が偏平状を呈し２μｍ以下の粒度分布が５
０％以上、５μｍ以上の粒度分布が１０％以下のもの
で、平均粒子径が１〜３μm 程度のもので、嵩比容積が
２．０〜３．０（ｍｌ／ｇ）程度のもの（日本タルク
製：ミクロエースＰ−３、ミクロエースＰ−４など）が
好ましい。この範囲を越えると塗膜の表面荒れが生じた
り屈曲した時に亀裂が発生したり、折り曲げ部が白化し
たりするので好ましくない。The talc used in the present invention has flat particles and a particle size distribution of 2 μm or less is 5
Those having a particle size distribution of 0% or more and 5 μm or more and 10% or less, an average particle diameter of about 1 to 3 μm, and a bulk specific volume of about 2.0 to 3.0 (ml / g) (Japan Talc: Microace P-3, Microace P-4, etc.) are preferred. If it exceeds this range, the surface of the coating film may be roughened, cracks may occur when the coating film is bent, or the bent portion may be whitened, which is not preferable.
【００４４】この発明において、タルクの使用量は、ポ
リイミドシロキサン１００重量部に対して、２〜１５０
重量部、好ましくは５〜１５０重量部、さらに好ましく
は１０〜１００重量部、その中でも特に好ましくは１０
〜８０重量部である。使用量が、余り多すぎたり、余り
少なすぎると塗膜の折り曲げによりクラックが発生した
り、半田耐熱性が悪くなるので上記範囲が好ましい。In the present invention, the amount of talc used is 2 to 150 with respect to 100 parts by weight of polyimide siloxane.
Parts by weight, preferably 5 to 150 parts by weight, more preferably 10 to 100 parts by weight, and particularly preferably 10
~ 80 parts by weight. If the amount used is too large or too small, cracks may occur due to bending of the coating film and solder heat resistance may deteriorate, so the above range is preferred.
【００４５】また、シリコン系の増粘度成分、例えば日
本アエロジル製：アエロジル等をポリイミドシロキサン
１００重量部に対して好ましくは１〜５０重量部、特に
５〜４０重量部添加することが好ましい。Further, it is preferable to add a silicon-based viscosity increasing component, for example, Aerosil manufactured by Nippon Aerosil Co., Ltd., to 1 to 50 parts by weight, particularly 5 to 40 parts by weight, based on 100 parts by weight of the polyimidesiloxane.
【００４６】この発明において、ポリイミドシロキサン
の溶液組成物は、ポリイミドシロキサン、エポキシ樹
脂、及びタルク各所定量を均一に、攪拌・混合すること
によって容易に得ることができる。混合する際、適当な
有機極性溶媒中で混合し、ポリイミドシロキサンの溶液
組成物にすることができる。溶媒に溶解させた溶液組成
物にするにあたっては、混合後行ってもよい。ポリイミ
ドシロキサンは、ポリイミドシロキサンの重合溶液をそ
のままでも、又その重合溶液を適当な有機溶媒で希釈し
たものであってもよい。有機極性溶媒としては、前記ポ
リイミドシロキサンを得る際に使用できる有機極性溶媒
を挙げることができるが、沸点１４０℃以上のものがよ
く、例えば沸点１８０℃以上、特に２００℃以上である
有機溶媒（例えばメチルトリグライムなど）を使用する
と、溶媒の蒸発による散逸が極めて減少するので、保存
安定性がよくなったり、又その印刷インクを使用してス
クリーン印刷を支障なく好適に行うことができるので最
適である。In the present invention, the solution composition of polyimidesiloxane can be easily obtained by uniformly stirring and mixing predetermined amounts of polyimidesiloxane, epoxy resin and talc. Upon mixing, they can be mixed in a suitable organic polar solvent to form a solution composition of polyimidesiloxane. The solution composition dissolved in the solvent may be mixed and then mixed. The polyimide siloxane may be the polyimide siloxane polymerization solution as it is, or the polymerization solution diluted with an appropriate organic solvent. Examples of the organic polar solvent include organic polar solvents that can be used when obtaining the polyimidesiloxane, but those having a boiling point of 140 ° C. or higher are preferable, for example, an organic solvent having a boiling point of 180 ° C. or higher, particularly 200 ° C. or higher (for example, Methyl triglyme, etc.) is extremely suitable because the dissipation due to evaporation of the solvent is greatly reduced, and the storage stability is improved, and the printing ink can be used for screen printing without any problems. is there.
【００４７】上記ポリイミドシロキサンの溶液組成物の
濃度は、５〜６０重量％、好ましくは５〜５０重量％、
そのなかでも特に１０〜４５重量％が適当であり、上記
溶液粘度は、０．０１〜１０，０００ポイズ、好ましく
は０．１〜１，０００ポイズであることが作業性や溶液
物性、その保護膜特性上などから適当である。The concentration of the polyimide siloxane solution composition is 5 to 60% by weight, preferably 5 to 50% by weight,
Among them, 10 to 45% by weight is particularly suitable, and the solution viscosity is 0.01 to 10,000 poise, preferably 0.1 to 1,000 poise, workability, solution physical properties, and protection thereof. It is suitable from the viewpoint of film characteristics.
【００４８】この発明のポリイミドシロキサンの組成物
から形成された保護膜は、優れた機械強度、電気絶縁性
を保持していると共に、耐熱性及び耐薬品性（耐ハンダ
フラックス性、耐スズメッキ液性）も高いので種々の電
気又は電子部品（特にフレキシブル配線板）の表面保護
膜や層間絶縁膜などとして好適に使用できる。被覆すべ
き対象物（フレキシブル回路板、半導体など）の表面
に、常温又は加温下、回転塗布機、ディスペンサー又は
印刷機などを使用する塗布方法で均一な厚さに塗布し、
前記溶液組成物からなる塗布膜を形成し、次いでその塗
布膜を５０℃以上、好ましくは約１１０℃以上、特に１
２０〜１８０℃程度の温度で乾燥させることにより、固
化膜（保護膜、厚さ：約０．５〜５００μｍ程度）を形
成することができる。The protective film formed from the composition of the polyimidesiloxane of the present invention retains excellent mechanical strength and electrical insulation, and also has heat resistance and chemical resistance (solder flux resistance, tin plating solution resistance). ) Is high, it can be suitably used as a surface protective film or an interlayer insulating film for various electric or electronic parts (particularly flexible wiring boards). Apply to the surface of the object to be coated (flexible circuit board, semiconductor, etc.) at room temperature or under heating at a uniform thickness by a coating method using a spin coater, dispenser or printing machine,
A coating film composed of the solution composition is formed, and then the coating film is heated to 50 ° C. or higher, preferably about 110 ° C. or higher, especially 1
By drying at a temperature of about 20 to 180 ° C., a solidified film (protective film, thickness: about 0.5 to 500 μm) can be formed.
【００４９】[0049]
【実施例】以下、実施例及び比較例を示し、この発明を
説明する。各例において測定、評価は次の方法で行っ
た。EXAMPLES The present invention will be described below with reference to Examples and Comparative Examples. The measurement and evaluation in each example were carried out by the following methods.
【００５０】以下の各例で使用した化合物をその略号と
共に以下に示す。 ａ−ＢＰＤＡ：２、３、３’、４’−ビフェニルテトラ
カルボン酸二無水物 ＢＴＤＡ：３、３’、４、４’−ベンゾフェノンテトラ
カルボン酸二無水物 ＰＭＤＡ：ピロメリット酸二無水物 ＥＴＤＡ：３、３’、４、４’−ジフェニルエ−テルテ
トラカルボン酸二無水物 ＤＳＤＡ：３、３’、４、４’−ジフェニルスルホンテ
トラカルボン酸二無水物 ６ＦＤＡ：２、２−ビス（３、４−ベンゼンジカルボン
酸無水物）ヘキサフルオオロプロパン ＰＳＩ：α、ω−ビス（３−アミノプロピル）ポリジメ
チルシロキサン ＤＡＢＡ：３、５−ジアミノ安息香酸 ＨＡＢ：３、３’−ジハイドロキシ−４、４’−ジアミ
ノビフェニル ＭＢＡＡ：ビス（３−カルボキシ、４−アミノフェニ
ル）メタン ＭＢＨＡ：ビス（３−ハイドロキシ、４−アミノフェニ
ル）メタン ＦＦ：２、２−ビス（４−ハイドロキシ、３−アミノフ
ェニル）ヘキサフルオロプロパン ＤＡＤＥ：４、４’−ジアミノジフェニルエ−テル ＴＰＥＱ：１、４−（４−アミノフェノキシ）ベンゼン ＢＡＰＰ：２、２−ビス〔４−（４−アミノフェノキ
シ）フェニル〕プロパン ＴＧ：トリグライム ＮＭＰ：Ｎ−メチル−２−ピロリドンThe compounds used in the following examples are shown below together with their abbreviations. a-BPDA: 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride BTDA: 3,3', 4,4'-benzophenonetetracarboxylic dianhydride PMDA: pyromellitic dianhydride ETDA: 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride DSDA: 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride 6FDA: 2,2-bis (3, 4-benzenedicarboxylic acid anhydride) hexafluoropropane PSI: α, ω-bis (3-aminopropyl) polydimethylsiloxane DABA: 3,5-diaminobenzoic acid HAB: 3,3′-dihydroxy-4,4 '-Diaminobiphenyl MBAA: Bis (3-carboxy, 4-aminophenyl) methane MBHA: Bis (3-hydroxy, 4-aminophenyl) methane FF: 2,2-bis (4-hydroxy, 3-aminophenyl) hexafluoropropane DADE: 4,4'-diaminodiphenylether TPEQ: 1,4- (4-aminophenoxy) benzene BAPP: 2,2 -Bis [4- (4-aminophenoxy) phenyl] propane TG: triglyme NMP: N-methyl-2-pyrrolidone
【００５１】〔対数粘度（ηｉｎｈ）の測定〕ポリイミ
ドシロキサン反応液の対数粘度（ηｉｎｈ）は、次式に
よって表すことが出来る。 ηｉｎｈ＝ｌｎ（ｔ／ｔ0 ）／ｃ 但し、ｔは測定溶液のキャノンフェンスケ粘度計におけ
る標線間の通過時間（秒）、ｔ0 は純溶媒のキャノンフ
ェンスケ粘度計における標線間の通過時間（秒）、ｃは
ポリイミドシロキサン固形物の濃度（ｇ／１００ｍｌ溶
媒）を表す。粘度の測定は、３０℃、Ｎ−メチル−２−
ピロリドン溶媒を用いて、ポリイミドシロキサン固形物
濃度０．５ｇ／１００ｍｌで行った。[Measurement of Logarithmic Viscosity (ηinh)] The logarithmic viscosity (ηinh) of the polyimidesiloxane reaction solution can be represented by the following equation. ηinh = ln (t / t 0 ) / c where, t is the transit time between the marked lines in the Cannon-Fenske viscometer measurement solution (in seconds), t 0 is between the marked lines in the Cannon-Fenske viscometer of pure solvent The passage time (seconds) and c represent the concentration of the polyimidesiloxane solid (g / 100 ml solvent). Viscosity is measured at 30 ° C., N-methyl-2-
A pyrrolidone solvent was used at a polyimide siloxane solid concentration of 0.5 g / 100 ml.
【００５２】〔平均粒子径の測定方法〕タルクの平均粒
子径は遠心沈降法により求めた。 使用したタルクは日本タルク製：ＭＳ−Ｐ（平均粒子
径：１０μｍ）、ミクロエ−スＫ−１（平均粒子径：
３．２μｍ）、ミクロエ−スＰ−２（平均粒子径：２．
３μｍ）、ミクロエ−スＰ−３（平均粒子径：１．８μ
ｍ）、ミクロエ−スＰ−４（平均粒子径：１．５μｍ）
である。[Measurement Method of Average Particle Diameter] The average particle diameter of talc was determined by the centrifugal sedimentation method. Talc used was manufactured by Nippon Talc: MS-P (average particle size: 10 μm), Microace K-1 (average particle size:
3.2 μm), Microace P-2 (average particle size: 2.
3 μm), Microace P-3 (average particle size: 1.8 μm
m), Microace P-4 (average particle size: 1.5 μm)
Is.
【００５３】〔ハンダ（半田）耐熱性の測定方法〕厚さ
３５μｍの電解銅箔の光沢面に厚さ５０μｍのポリイミ
ド製スペ−サ−をのせ、ポリイミドシロキサン混合物
（組成物）を流延し、８０℃で３０分、１６０℃で６０
分加熱乾燥を行い、ポリイミドシロキサン混合物の保護
膜を形成した。ポリイミドシロキサン保護膜を形成した
銅箔を３×３ｃｍに切断し、保護膜上にロジン系フラッ
クス（サンワ化学工業製：ＳＵＮＦＬＵＸ ＳＦ−２７
０）を塗布した後、２６０℃の溶融半田浴に３０秒間保
護膜面を接触させ、冷却後、保護膜のふくれの有無を観
察し、評価した。 ○：全くふくれなし、△：僅かにふくれあり、×：ふく
れあり[Measurement method of solder (solder) heat resistance] A polyimide spacer having a thickness of 50 μm is placed on a glossy surface of an electrolytic copper foil having a thickness of 35 μm, and a polyimidesiloxane mixture (composition) is cast. 30 minutes at 80 ℃, 60 at 160 ℃
The film was heated and dried for a minute to form a protective film of the polyimidesiloxane mixture. A copper foil having a polyimidesiloxane protective film formed thereon was cut into 3 × 3 cm, and a rosin-based flux (SUNFLUX SF-27 manufactured by Sanwa Chemical Industry Co., Ltd.) was formed on the protective film.
After applying 0), the protective film surface was brought into contact with a molten solder bath at 260 ° C. for 30 seconds, and after cooling, the presence or absence of swelling of the protective film was observed and evaluated. ○: No blistering, △: Slight blistering, ×: Blistering
【００５４】〔銅箔変色性の測定方法〕厚さ３５μｍの
電解銅箔の光沢面に厚さ７５μｍのポリイミド製スペ−
サ−を使用して、ポリイミドシロキサン混合物（組成
物）を流延し、８０℃で３０分、１６０℃で６０分加熱
乾燥を行った。５〜４０μｍの不均一な厚みを持ったポ
リイミドシロキサン混合物の保護膜を形成した銅箔を２
×１０ｃｍの大きさに切断し、７０℃に加熱したスズメ
ッキ浴（シプレイ・ファ−イ−スト株式会社ティンポジ
ットＬＴ−３４）に５分間浸漬した。その後、７０℃以
上の熱水で５分間洗浄を行い乾燥させた。５〜４０μｍ
の厚さを持ったポリイミドシロキサン保護膜を形成した
側の銅箔上に一部変色する部分が認められた。その変色
部分の保護膜の厚さが２０μｍ未満の場合を○、保護膜
厚さ２０μｍ以上の場合を×と判定した。[Measurement Method of Copper Foil Discoloration Property] A 75 μm-thick polyimide spacer is applied to the glossy surface of an electrolytic copper foil having a thickness of 35 μm.
The polyimide siloxane mixture (composition) was cast using a heater and heat-dried at 80 ° C. for 30 minutes and 160 ° C. for 60 minutes. Two copper foils with a protective film of a polyimidesiloxane mixture having a non-uniform thickness of 5-40 μm were formed.
It was cut into a size of × 10 cm and immersed in a tin plating bath (Shipley Fast East Co., Ltd., Tinposit LT-34) heated to 70 ° C. for 5 minutes. Then, it was washed with hot water at 70 ° C. or higher for 5 minutes and dried. 5-40 μm
Partly discolored portion was observed on the copper foil on the side where the polyimide siloxane protective film having a thickness of 3 was formed. When the thickness of the protective film in the discolored portion was less than 20 μm, it was judged as ◯, and when the protective film thickness was 20 μm or more, it was judged as x.
【００５５】〔密着性〕厚さ３５μｍの電解銅箔の粗面
又は厚さ７５μｍのポリイミドフィルム上にスペ−サ−
等を使用して、ポリイミドシロキサン混合物（組成物）
を流延し、８０℃で３０分、１５０℃で６０分加熱乾燥
を行い、ポリイミドシロキサンの混合物の膜厚が２０〜
３０μｍの保護膜を形成した。保護膜面が外側になるよ
うにポリイミドフィルムを折り曲げ、折り曲げ部の山を
５０倍の顕微鏡で観察し亀裂の有無を判定した。 ○：全く亀裂なし、△：折り曲げ部白化、×：亀裂あり[Adhesion] A spacer was formed on a rough surface of an electrolytic copper foil having a thickness of 35 μm or on a polyimide film having a thickness of 75 μm.
Polyimide siloxane mixture (composition) using etc.
And heat-dried at 80 ° C. for 30 minutes and 150 ° C. for 60 minutes to give a polyimide siloxane mixture having a film thickness of 20 to
A 30 μm protective film was formed. The polyimide film was bent so that the protective film surface was on the outside, and the crests of the bent portion were observed with a microscope of 50 times to determine the presence or absence of cracks. ◯: No cracks at all, Δ: Whitening at bent portions, ×: Cracks
【００５６】〔ポリイミドシロキサンの製造〕 参考例１ 容量２０リットルのガラス製フラスコに、2,3,3',4'-ビ
フェニルテトラカルボン酸二無水物 ２９４．２２ｇ、
トリグライム ７００ｇを仕込み、室温で撹拌しながら
溶解した後、α、ω−ビス（3-アミノプロピル）ポリジ
メチルシロキサン（信越シリコン製、Ｘ−２２−１６１
ＡＳ、ｎ＝９） ６０５．３０ｇとトリグライム １８
５ｇを加えて均一に溶解させ、窒素雰囲気下に、１８５
℃に加熱してこの温度を維持しながら４時間重合した。
次いで反応液を室温に戻してして撹拌しながら２、２−
ビス〔４−（４−アミノフェノキシ) フェニル] プロパ
ン６２．２０ｇと３、５−ジアミノ安息香酸 ２３．０
５ｇ及びトリグライム５０９ｇを加えた後、反応温度を
１８５℃にあげて更に４時間反応させてポリイミドシロ
キサン溶液を製造した。このイミドシロキサンは濃度が
４０．５重量％、溶液粘度が２１ポイズであった。又、
このようにして得られたポリイミドシロキサンは、収率
が９９％、分子量の目安として対数粘度が０．２３であ
り、イミド化率が実質的に１００％であった。[Production of Polyimide Siloxane] Reference Example 1 In a glass flask having a capacity of 20 liters, 2,942,2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 294.22 g,
After 700 g of triglyme was charged and dissolved at room temperature with stirring, α, ω-bis (3-aminopropyl) polydimethylsiloxane (manufactured by Shin-Etsu Silicon Co., Ltd., X-22-161
AS, n = 9) 605.30 g and triglyme 18
5 g was added and dissolved uniformly, and under a nitrogen atmosphere, 185
Polymerization was carried out for 4 hours while heating at 0 ° C and maintaining this temperature.
Then, the reaction solution is returned to room temperature and stirred for 2,2-
62.20 g of bis [4- (4-aminophenoxy) phenyl] propane and 3,5-diaminobenzoic acid 23.0
After adding 5 g and 509 g of triglyme, the reaction temperature was raised to 185 ° C. and the reaction was further continued for 4 hours to prepare a polyimidesiloxane solution. This imidosiloxane had a concentration of 40.5% by weight and a solution viscosity of 21 poise. or,
The polyimidesiloxane thus obtained had a yield of 99%, a logarithmic viscosity of 0.23 as a measure of the molecular weight, and an imidization ratio of substantially 100%.
【００５７】参考例２ 容量５００ｍｌのガラス製フラスコに、ａ−ＢＰＤＡ４
４．１ｇ（１５０ミリモル）、トリグライム１００ｇを
仕込み、窒素雰囲気下、１８０℃で撹拌加熱した。α、
ω−ビス（３−アミノプロピル）ポリジメチルシロキサ
ン（アミノ当量３７０、ｎ＝７．６）７７．７ｇ、トリ
グライム５０ｇを加え、１８５℃で６０分間加熱した。
さらにこの反応溶液にＤＡＢＡ３．４ｇ、ＢＡＰＰ９．
２ｇ、及びトリグライム３６ｇを加え１８０℃で６時間
加熱攪拌した後、濾過を行った。得られたポリイミドシ
ロキサン反応溶は、イミドシロキサン固形分濃度が４１
重量％、ηｉｎｈ ０．２８、溶液粘度 ４０ポイズの
均一な溶液であった。イミド化率は実質的に１００％で
あった。Reference Example 2 In a glass flask having a volume of 500 ml, a-BPDA4 was added.
4.1 g (150 mmol) and 100 g of triglyme were charged, and the mixture was heated with stirring at 180 ° C. under a nitrogen atmosphere. α,
77.7 g of ω-bis (3-aminopropyl) polydimethylsiloxane (amino equivalent 370, n = 7.6) and 50 g of triglyme were added, and the mixture was heated at 185 ° C. for 60 minutes.
Furthermore, 3.4 g of DABA, BAPP9.
2 g and 36 g of triglyme were added, and the mixture was heated with stirring at 180 ° C. for 6 hours and then filtered. The resulting polyimide siloxane reactive solution had an imide siloxane solid concentration of 41.
It was a uniform solution having a weight% of ηinh of 0.28 and a solution viscosity of 40 poises. The imidization ratio was substantially 100%.
【００５８】参考例３〜２３ 表１に示した酸二無水物とジアミン成分とを使用した以
外は参考例２と同様にして表１に示したポリイミドシロ
キサン反応液を得た。参考例２１だけは１０００ｍｌの
ガラス容器を用いて行った。Reference Examples 3 to 23 Polyimide siloxane reaction solutions shown in Table 1 were obtained in the same manner as in Reference Example 2 except that the acid dianhydride and the diamine component shown in Table 1 were used. Only Reference Example 21 was carried out using a 1000 ml glass container.
【００５９】実施例１ ガラス製容器に、参考例１で得たポリイミドシロキサン
溶液１００ｇ、エポキシ樹脂（油化シェル社製、エピコ
ート１５７Ｓ−７０） ７．２０ｇとタルク２１．４ｇ
（日本タルク社製：ミクロエースＰ−３，平均粒子径
１．８μm ，嵩比容積２．０〜２．６ｍｌ／ｇ）とを仕
込み、室温（２５℃）で、２時間攪拌して、均一に溶解
させたポリイミドシロキサンの溶液組成物（溶液粘度：
１８０ポイズ）を得た。この溶液組成物を用いて上記の
半田耐熱性、銅箔変色性、屈曲性、密着性をそれぞれ測
定した。この溶液組成物は、１週間室温に放置しても、
均一な溶液の状態・粘度を保持していた。結果を第１
表、表２に示す。Example 1 In a glass container, 100 g of the polyimidesiloxane solution obtained in Reference Example 1, 7.20 g of epoxy resin (Epicote 157S-70 manufactured by Yuka Shell Co., Ltd.) and 21.4 g of talc were used.
(Manufactured by Nippon Talc Co., Ltd .: Microace P-3, average particle diameter 1.8 μm, bulk specific volume 2.0 to 2.6 ml / g), and stirred at room temperature (25 ° C.) for 2 hours to homogenize Solution composition of polyimidesiloxane dissolved in (solution viscosity:
180 poise). Using this solution composition, the solder heat resistance, the copper foil discoloration property, the bending property, and the adhesion property were measured. This solution composition, even if left at room temperature for 1 week,
It maintained a uniform solution state and viscosity. First result
The results are shown in Table and Table 2.
【００６０】実施例２〜３３ 表２及び表３に示す種類と量のポリイミドシロキサン反
応液、エポキシ樹脂、タルクを使用した以外は実施例１
と同様にして、ポリイミドシロキサンの溶液組成物を製
造した。それぞれ上記の半田耐熱性、銅箔変色性、屈曲
性、密着性を測定した。結果を表２、表３に示す。Examples 2-33 Example 1 except that the type and amount of polyimidesiloxane reaction liquid, epoxy resin and talc shown in Tables 2 and 3 were used.
A solution composition of polyimide siloxane was produced in the same manner as. The solder heat resistance, copper foil discoloration, bendability, and adhesiveness described above were measured, respectively. The results are shown in Tables 2 and 3.
【００６１】比較例１〜３５ 表４及び表５に示す種類と量の各成分を使用した以外は
実施例１と同様にしてポリイミドシロキサンの溶液組成
物を製造した。それぞれ上記の半田耐熱性、銅箔変色
性、屈曲性、密着性を測定した。結果を表４、表５に示
す。Comparative Examples 1 to 35 Polyimide siloxane solution compositions were produced in the same manner as in Example 1 except that the types and amounts of the components shown in Tables 4 and 5 were used. The solder heat resistance, copper foil discoloration, bendability, and adhesiveness described above were measured, respectively. The results are shown in Tables 4 and 5.
【００６２】[0062]
【表１】 [Table 1]
【００６３】[0063]
【表２】 [Table 2]
【００６４】[0064]
【表３】 [Table 3]
【００６５】[0065]
【表４】 [Table 4]
【００６６】[0066]
【表５】 [Table 5]
【００６７】[0067]
【発明の効果】この発明の可溶性のポリイミドシロキサ
ン、エポキシ樹脂、及びタルクを含有してなるポリイミ
ドシロキサンの組成物は、耐熱性、密着性、耐薬品性
（特に耐ハンダフラックス性、耐スズメッキ液性）及び
貯蔵安定性に優れ、フレキシブル配線板上にスクリーン
印刷などで保護膜の形成が可能である。そして印刷用イ
ンキ、塗布用ワニスなどの溶液組成物として好適に使用
されうる。INDUSTRIAL APPLICABILITY The composition of polyimide siloxane containing soluble polyimide siloxane, epoxy resin and talc of the present invention has heat resistance, adhesion and chemical resistance (especially solder flux resistance, tin plating solution resistance). ) And storage stability, a protective film can be formed on a flexible wiring board by screen printing or the like. Then, it can be suitably used as a solution composition such as a printing ink or a coating varnish.
【００６８】この発明のポリイミドシロキサンの組成物
は、その溶液組成物をシリコンウエハー、フレキシブル
配線基板などに塗布し、乾燥・硬化して、保護膜を形成
した場合に、実質的にカールを引き起こすことがなく、
又その保護膜が優れた耐屈曲性、耐半田性( 耐熱性) を
有すると共に、特に基板への密着性が優れ、シランカッ
プリング剤などの密着促進剤で予め基板の前処理をする
必要がないので、例えば、ＩＣ，ＬＳＩのパッシベーシ
ョン膜や、ダイオードのジャンクションコートなどの用
途に上記前処理を行うことなく優れた保護膜を形成する
ことができる。The composition of the polyimidesiloxane of the present invention causes curl substantially when the solution composition is applied to a silicon wafer, a flexible wiring board, etc., and dried and cured to form a protective film. Without
In addition, the protective film has excellent bending resistance and solder resistance (heat resistance), and also has excellent adhesion to the substrate, and it is necessary to pretreat the substrate in advance with an adhesion promoter such as a silane coupling agent. Therefore, for example, an excellent protective film can be formed without performing the above pretreatment for applications such as IC and LSI passivation films and junction coating of diodes.
フロントページの続き (72)発明者 志水 幸男 山口県宇部市大字小串1978の６ 宇部興産 株式会社宇部ケミカル工場内Front page continued (72) Inventor Yukio Shimizu 6 1978, Kogushi, Ube, Yamaguchi Prefecture Ube Industries Ltd. Ube Chemical Factory Co., Ltd.
Claims (2)
トラカルボン酸を除く４価の残基を示し、Ｒ２は一般式
（４）のジアミノポリシロキサンのアミノ基を除く２価
の残基を示し、Ｒ３は一般式（５）で示される芳香族ジ
アミン化合物よりアミノ基を除く２価の残基を示し、Ｒ
４は一般式（４）及び一般式（５）で示されるジアミン
化合物を除くジアミン化合物からアミノ基を除く２価の
残基を示し、ｎ１は３〜３０の整数を示し、Ｒ５は２価
の炭化水素基又はフェニル基を示し、Ｒ６は独立に炭素
数１〜３のアルキル基またはフェニル基を示し、×は直
接結合又は一般式（６）で示し、ｒ１は水酸基又はカル
ボキシル基を示し、ｎ２は１又は２の整数を示し、ｎ３
は０〜３の整数を示し、Ｒ７、Ｒ８は水素、メチル基又
はハロゲン化メチル基を示し、ｍ１、ｍ２及びｍ３の割
合が各成分合計１００モル％中ｍ１が４５〜８０モル
％、ｍ２が０．５〜４０モル％及びｍ３が残部であ
る。） 一般式（４） 【化４】 一般式（５） 【化５】 一般式（６） 【化６】 で示される有機溶剤可溶性のポリイミドシロキサン１０
０重量部、（ｂ）エポキシ樹脂１〜５０重量部、（ｃ）
２〜１５０重量部のその粒子が偏平状で平均粒子径が１
〜３μm のタルクからなることを特徴とするポリイミド
シロキサンの組成物。(A) General formula (1): General formula (2) And the general formula (3): (In the formula, R1 represents a tetravalent residue excluding tetracarboxylic acid from aromatic tetracarboxylic acid, and R2 represents a divalent residue excluding amino group of diaminopolysiloxane of the general formula (4). , R3 represents a divalent residue excluding an amino group from the aromatic diamine compound represented by the general formula (5), and R3
4 represents a divalent residue excluding an amino group from a diamine compound other than the diamine compounds represented by the general formulas (4) and (5), n1 represents an integer of 3 to 30, and R5 represents a divalent compound. Represents a hydrocarbon group or a phenyl group, R6 independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, x represents a direct bond or is represented by the general formula (6), r1 represents a hydroxyl group or a carboxyl group, and n2 Is an integer of 1 or 2 and n3
Represents an integer of 0 to 3, R7 and R8 represent hydrogen, a methyl group or a halogenated methyl group, and the proportion of m1, m2 and m3 is 45 to 80 mol% and m2 is 100 to 100 mol% in total of each component. The balance is 0.5 to 40 mol% and m3. ) General formula (4) General formula (5) General formula (6) Organic solvent-soluble polyimide siloxane 10
0 parts by weight, (b) 1 to 50 parts by weight of epoxy resin, (c)
2 to 150 parts by weight of the particles are flat and have an average particle size of 1
A composition of a polyimide siloxane, characterized in that it comprises talc of 3 μm.
トラカルボン酸を除く４価の残基を示し、Ｒ２は一般式
（４）のジアミノポリシロキサンのアミノ基を除く２価
の残基を示し、Ｒ３は一般式（５）で示される芳香族ジ
アミン化合物よりアミノ基を除く２価の残基を示し、Ｒ
４は一般式（４）及び一般式（５）で示されるジアミン
化合物を除くジアミン化合物からアミノ基を除く２価の
残基を示し、ｎ１は３〜３０の整数を示し、Ｒ５は２価
の炭化水素基又はフェニル基を示し、Ｒ６は独立に炭素
数１〜３のアルキル基またはフェニル基を示し、×は直
接結合又は一般式（６）で示し、ｒ１は水酸基又はカル
ボキシル基を示し、ｎ２は１又は２の整数を示し、ｎ３
は０〜３の整数を示し、Ｒ７、Ｒ８は水素、メチル基又
はハロゲン化メチル基を示し、ｍ１、ｍ２及びｍ３の割
合が各成分合計１００モル％中ｍ１が４５〜８０モル
％、ｍ２が０．５〜４０モル％及びｍ３が残部であ
る。） 一般式（４） 【化１０】 一般式（５） 【化１１】 一般式（６） 【化１２】 で示される有機溶剤可溶性のポリイミドシロキサン１０
０重量部、（ｂ）エポキシ樹脂１〜５０重量部、（ｃ）
２〜１５０重量部のその粒子が偏平状で平均粒子径が１
〜３μm のタルクを含有するポリイミドシロキサンの組
成物を加熱してなることを特徴とする硬化物。2. (a) General formula (1): General formula (2) And the general formula (3): (In the formula, R1 represents a tetravalent residue excluding tetracarboxylic acid from aromatic tetracarboxylic acid, and R2 represents a divalent residue excluding amino group of diaminopolysiloxane of the general formula (4). , R3 represents a divalent residue excluding an amino group from the aromatic diamine compound represented by the general formula (5), and R3
4 represents a divalent residue excluding an amino group from a diamine compound other than the diamine compounds represented by the general formulas (4) and (5), n1 represents an integer of 3 to 30, and R5 represents a divalent compound. Represents a hydrocarbon group or a phenyl group, R6 independently represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, x represents a direct bond or is represented by the general formula (6), r1 represents a hydroxyl group or a carboxyl group, and n2 Is an integer of 1 or 2 and n3
Represents an integer of 0 to 3, R7 and R8 represent hydrogen, a methyl group or a halogenated methyl group, and the proportion of m1, m2 and m3 is 45 to 80 mol% and m2 is 100 to 100 mol% in total of each component. The balance is 0.5 to 40 mol% and m3. ) General formula (4): General formula (5) General formula (6) Organic solvent-soluble polyimide siloxane 10
0 parts by weight, (b) 1 to 50 parts by weight of epoxy resin, (c)
2 to 150 parts by weight of the particles are flat and have an average particle size of 1
A cured product obtained by heating a composition of a polyimide siloxane containing talc of 3 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07059045A JP3136942B2 (en) | 1994-03-18 | 1995-03-17 | Polyimide siloxane composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4867294 | 1994-03-18 | ||
| JP6-48672 | 1994-03-18 | ||
| JP07059045A JP3136942B2 (en) | 1994-03-18 | 1995-03-17 | Polyimide siloxane composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07304950A true JPH07304950A (en) | 1995-11-21 |
| JP3136942B2 JP3136942B2 (en) | 2001-02-19 |
Family
ID=26388976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07059045A Expired - Lifetime JP3136942B2 (en) | 1994-03-18 | 1995-03-17 | Polyimide siloxane composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3136942B2 (en) |
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| JP2002012666A (en) * | 2000-06-29 | 2002-01-15 | Shin Etsu Chem Co Ltd | Polyimidesilicone resin, method for producing the same and composition thereof |
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