JP4377354B2 - Polyimide silicone resin composition - Google Patents

Description

  The present invention relates to a polyimide silicone resin composition suitable for use in electrode protection of electronic parts.

  Conventionally, a polyimide resin having excellent heat resistance and electrical / mechanical characteristics has been used as a resin for an insulating protective film of an electronic component or the like. When forming a protective film, since polyimide resin is generally insoluble in organic solvents, a solution of polyamic acid, which is a precursor thereof, is applied to a substrate, and then heated and closed by a dehydration condensation reaction. A method of forming a polyimide resin film is adopted.

  However, in the method using this polyamic acid solution, the viscosity of the polyamic acid solution is very high, so that the workability is inferior, and it is necessary to make the temperature higher than 300 ° C. in the dehydration condensation process, and the obtained polyimide resin The coating had problems such as poor adhesion to substrates such as nickel, aluminum, silicon, and silicon oxide film.

  In order to improve such problems of conventional polyimide, a method using polyimide silicone obtained by replacing a part of the diamine component which is a raw material of polyimide with a diamine having a siloxane structure (see Patent Document 1 and Patent Document 2) It has been known. Polyimide silicone is widely used in the electronic / electrical industry as a material for forming a surface protective film for electronic parts and as an interlayer insulating material for electronic parts and other heat-resistant parts. Polyimide silicone is used for coating the surface of a substrate by coating or patterning, and is a material for electronic components that combines high heat resistance derived from a polyimide structure and low elastic modulus derived from a silicone structure. Since the moisture permeability is higher than polyimide that does not contain water, moisture easily reaches the interface between the electrode and the polyimide silicone, and when ionic impurities are present, corrosion of the electrode occurs, causing problems in reliability. There was a case. Moreover, the further improvement was also desired about adhesiveness with a base material.

  Regarding the problem caused by the presence of the ionic impurities, it has been proposed to blend an ion exchange resin or a chelate resin in polyimide silicone as an undercoat resin (see Patent Document 3). As a result, impurity ions in the epoxy resin layer, which is an overcoat resin, are trapped, ions do not reach the vicinity of the semiconductor surface, and high voltage diodes with high breakdown voltage and low leakage current can be produced stably with high yield. ing. However, it was revealed that the ion exchange resin or the chelate resin itself decomposes under high temperature conditions in an endurance test, and as a result of the presence of ionic species on the electrode surface, corrosion of the electrode occurs. Further, since the ion exchange resin swells with a solvent, it has been clarified that the removal of the solvent in the subsequent process becomes insufficient, and as a result, the mechanical strength of the resin is lowered and the electrical characteristics are deteriorated.

Moreover, the present applicant has proposed to obtain a composition suitable for electrode protection by blending an inorganic ion exchanger with polyimide silicone (Patent Document 4). However, this composition was not satisfactory in terms of adhesion to the substrate and electrode corrosion resistance.
Japanese Patent Publication No.43-27439 Japanese Patent Publication No.59-7213 Japanese Patent Laid-Open No. 10-294319 JP 2003-213129 A

  Then, the subject of this invention is providing the polyimide silicone resin composition suitable for the electrode protection use which is excellent in adhesiveness with a base material and excellent in narrow gap penetration property, without producing corrosion on the electrode surface. It is in.

  The present inventors have found that a novel reactive silyl group-containing bisimide compound having an imide ring and an alkoxysilyl group can be cured at room temperature, has excellent workability, and further has excellent heat resistance, mechanical strength, and electrical characteristics. A cured film having an excellent imide ring structure can be formed, and the cured film is excellent in adhesion to a substrate, excellent in solvent resistance, and also excellent in narrow gap penetration. It has been found that it can be suitably used as a material for protective films of parts and the like.

  In addition, the inventors have improved the adhesion of the polyimide silicone resin coating to the substrate by combining the reactive silyl group-containing bisimide compound, polyimide silicone resin and inorganic ion exchanger, and corroded the electrode surface. As a result of finding out that it is possible to obtain a polyimide silicone-based resin composition that does not cause the formation of the polymer, and based on this finding, the present invention has been completed.

That is, the present invention
(a) a polyamic acid which is a reaction product of a tetracarboxylic acid compound selected from the group consisting of an aromatic tetracarboxylic acid compound and an alicyclic tetracarboxylic acid compound, an aromatic diamine and a diaminosiloxane, and the polyamic acid A polymer selected from the group consisting of polyimide silicones which are ring-closing derivatives,
(b) solvent,
(c) Structural formula (1) below:

(1)
（式中、Ｒ¹は２価の有機基であり、Ｒ²およびＲ³は独立に非置換または置換の炭素原子数１〜10の１価炭化水素基であり、ｎは独立に１〜３の整数である）
で示される反応性シリル基含有ビスイミド化合物、および
(d) 無機イオン交換体： (a)成分100質量部に対して 0.5〜10質量部
を含有するポリイミドシリコーン系樹脂組成物を提供する。

(1)
(Wherein R ¹ is a divalent organic group, R ² and R ³ are independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is independently 1 to 3) Integer)
A reactive silyl group-containing bisimide compound represented by:
(d) Inorganic ion exchanger: (a) A polyimide silicone resin composition containing 0.5 to 10 parts by mass with respect to 100 parts by mass of the component is provided.

  The polyimide silicone resin composition of the present invention has a good adhesion strength to the substrate of the coating film formed by blending the reactive silyl group-containing bisimide compound and the inorganic ion exchanger, and the polyimide silicone resin Corrosion at the interface between the coating and the electrode can be prevented, it has excellent narrow gap penetration, and it does not generate corrosion on the electrode surface in durability tests under voltage application conditions, making it suitable for electrode protection applications. .

Hereinafter, the present invention will be described in detail.
[(A) Polymer]
[Tetracarboxylic acid compound]
The tetracarboxylic acid compound selected from the group consisting of the aromatic tetracarboxylic acid compound and the alicyclic tetracarboxylic acid compound used in the present invention includes tetracarboxylic acid, its monoanhydride, dianhydride, monoester, Derivatives such as diesters are included (hereinafter referred to as “tetracarboxylic acid component”).

  Preferable specific examples of this tetracarboxylic acid component include pyromellitic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetra Carboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1,3-bis (3, 4-Dicarboxyphenyl) -1,1,3,3, -tetramethyldisiloxane dianhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4 '-Diphenylmethanetetracarboxylic dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 3,3', 4,4 '-(2,2-diphenylpropane) tetracarboxylic acid Dianhydride, 3,3 ', 4,4'-(2,2-diphenylhexafluoropropane) tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4 -Bis (3,4-dicarboxypheno Xy) benzene dianhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, 1,1-bis [4- (3,4-dicarboxyphenoxy) phenyl] ethane dianhydride 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride , Cyclobutanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and the like; and corresponding to these tetracarboxylic dianhydrides Examples thereof include reactive derivatives such as tetracarboxylic acid, its ester, and diester. These can be used singly or in combination of two or more.

[Aromatic diamine]
Preferred examples of the aromatic diamine used in the present invention include 4,4′-diaminodiphenylmethane, o-, m-, p-phenylenediamine, bis [4- (3-aminophenoxy) phenyl] sulfone, 2 , 4-Diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 3,6-diaminodurene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl- 4,4'-diaminobiphenyl, 2,2'-dimethoxy-4,4'-diaminobiphenyl, 2,2'-diethoxy-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4 ' -Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 1,3-bis (3-aminophenoxy) benzene 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) Xy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-amino Phenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-amino-5-tri Fluoromethylphenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (3-amino- 4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexaflu Oropropane, 4,4'-bis (4-aminophenoxy) octafluorobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,5-diaminobenzotrifluoride, 2,5 -Diaminobenzotrifluoride, 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-bis (trifluoromethyl) -5,5'-diaminobiphenyl, 1,4- Bis (4-aminotetrafluorophenoxy) tetrafluorobenzene, 4,4'-bis (4-aminotetrafluorophenoxy) octafluorobiphenyl, 4,4'-diaminobinaphthyl, 4,4'-diaminobenzanilide, etc. It is done. These can be used singly or in combination of two or more.

[Diaminosiloxane]
Preferred examples of the diaminosiloxane used in the present invention include 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (4-aminobutyl). ) -1,1,3,3-tetramethyldisiloxane, bis (4-aminophenoxy) dimethylsilane, 1,3-bis (4-aminophenoxy) -1,1,3,3-tetramethyldisiloxane, etc. And the following general formula (2):
H ₂ N—Z— (SiR ₂ O) _m —SiR ₂ —Z—NH ₂ (2)
Wherein R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms other than an aliphatic unsaturated group, or 1 carbon atom. An alkoxy group of ˜8, an alkenoxy group or a cycloalkoxy group, Z is independently an unsubstituted or substituted divalent hydrocarbon group of 1 to 8 carbon atoms which may contain an ether bond in the chain; m is an integer of 1 to 100, preferably 3 to 60.)
The thing represented by is mentioned. These can be used singly or in combination of two or more.

  In the above general formula (2), when R is a monovalent hydrocarbon group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl Group, heptyl group, octyl group and other alkyl groups; vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, hexenyl group and other alkenyl groups; cyclopentyl group, cyclohexyl group and other cycloalkyl groups; Cycloalkenyl groups such as hexenyl groups; aryl groups such as phenyl groups, tolyl groups, xylyl groups; aralkyl groups such as benzyl groups, ethylphenyl groups, propylphenyl groups; and at least one of the hydrogen atoms of these groups is fluorine Substituted with halogen atoms such as atoms, chlorine atoms, bromine atoms, cyano groups, etc., for example, chloro Butyl group, 3-fluoropropyl group, 3,3,3-trifluoropropyl group, 4-fluorophenyl group, 2-cyanoethyl group and the like.

  Further, when R is an alkoxy group, alkenoxy group or cycloalkyloxy group, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, hexyloxy group, Examples thereof include a cyclohexyloxy group, an octoxy group, a vinyloxy group, an allyloxy group, a propeninoxy group, and an isopropenoxy group.

  In the general formula (2), examples of the divalent hydrocarbon group that may include an ether bond in the chain represented by Z include, for example, a methylene group, an ethylene group, a propylene group (trimethylene group), a methylethylene group (provided that With respect to the two groups contained in the general formula (2), an amino group is bonded to form a 2-amino-1-methylethyl group, or The amino group is bonded to form a 2-aminopropyl group), a tetramethylene group, a 2-methylpropylene group, and a 1-methylpropylene group (provided that two amino acids contained in the above general formula (2)). For the group, the amino group is bonded to form a 3-amino-1-methylpropyl group, or for the two groups, the amino group is a 3-aminobutyl group. To form), ethylethylene group (however, the above general formula (2) For the two included groups, the amino group is bonded to form a 1- (aminomethyl) propyl group, or for the two groups, the amino group is 2- An alkylene group such as a hexamethylene group and an octamethylene group; an arylene group such as an o-, m-, p-phenylene group and a tolylene group; an ether bond represented by the following formula: Examples thereof include an alkylene / arylene group which may be contained.

（但し、アミノ基は、上記３つの式中のベンゼン環に結合する）
上記一般式(2)で表わされるジアミノシロキサンの具体例としては、下記の化合物が挙げられるが、これに限定されるものではない。

(However, the amino group is bonded to the benzene ring in the above three formulas)
Specific examples of the diaminosiloxane represented by the general formula (2) include the following compounds, but are not limited thereto.

（ｍは、３〜60の整数）

(M is an integer from 3 to 60)

（ｍは、３〜60の整数）

(M is an integer from 3 to 60)

  The amount of diaminosiloxane used is a structure based on the diaminosiloxane in the polyimide silicone which is a polyamic acid or a ring-closing derivative thereof (that is, a polyamic acid produced by a reaction between a tetracarboxylic acid compound and diaminosiloxane or a polyimide unit in which the ring is closed) ) Is preferably 1 to 60% by mole, more preferably 10 to 50% by mole in all repeating units constituting the polyamic acid or polyimide silicone. If the structure based on diaminosiloxane is less than 1 mol%, the effect of imparting flexibility is poor, and if it exceeds 60 mol%, moisture permeability increases and a decrease in heat resistance is observed. For this purpose, it is preferable to use 1 to 60 mol%, more preferably 10 to 50 mol% of diaminosiloxane based on the total number of moles of the aromatic diamine and the diaminosiloxane.

[(B) Solvent]
As the solvent of the component (b), a solvent having a large dissolving power that is usually employed in the synthesis of polyamic acid or the like is employed. Preferred solvents include N-methylpyrrolidone; amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide; γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone, δ-valerolactone Lactones such as γ-caprolactone and ε-caprolactone; carbonates such as propylene carbonate; esters such as butyl acetate, ethyl cellosolve acetate and butyl cellosolve acetate; ethers such as dibutyl ether, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether; tetrahydrofuran Cyclic ethers such as methyl isobutyl ketone, cyclohexanone, acetophenone, etc .; alcohols such as butanol, octanol, ethyl cellosolve; chains such as dimethylformamide And cyclic amides, ureas, sulfoxides such as dimethyl sulfoxide, hydrocarbons such as sulfone, toluene, and halogen solvents such as chloroform and carbon tetrachloride. These can be used singly or in combination of two or more.

  The amount of the solvent used is not particularly limited as long as it does not affect the stability of the polyimide silicone resin composition and the penetration into the narrow gap. The amount is preferably in the range, and is usually 50 to 1900 parts by weight, preferably 100 to 1200 parts by weight, and more preferably about 150 to 900 parts by weight with respect to 100 parts by weight of component (a).

[(C) Reactive silyl group-containing bisimide compound]
The reactive silyl group-containing bisimide compound used in the present invention has the following structural formula (3):

(3)
で表されるアリル基含有酸無水物と、下記構造式(4)：
Ｈ₂Ｎ−Ｒ¹−ＮＨ₂ (4)
（式中、Ｒ¹は２価の有機基である）
で表される２官能性ジアミン化合物とを反応させて、
下記構造式(5)：

(3)
An allyl group-containing acid anhydride represented by the following structural formula (4):
H ₂ N—R ¹ —NH ₂ (4)
(Wherein R ¹ is a divalent organic group)
And a bifunctional diamine compound represented by
The following structural formula (5):

(5)
で示されるアリル基含有ビスイミド化合物を得て、次いで、下記一般式(6)：

(Five)
Then, an allyl group-containing bisimide compound represented by the following general formula (6):

(6)
（式中、Ｒ²およびＲ³は独立に非置換または置換の炭素原子数１〜10、好ましくは１〜６、より好ましくは１〜３の１価炭化水素基であり、ｎは１〜３の整数である）
で表され、ケイ素原子に結合した水素原子を１個有する有機シラン化合物とをヒドロシリル化反応により付加させることにより、下記一般式(1)：

(6)
Wherein R ² and R ³ are independently unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10, preferably 1 to 6, more preferably 1 to 3, and n is 1 to 3 Integer)
And an organic silane compound having one hydrogen atom bonded to a silicon atom, is added by a hydrosilylation reaction to give the following general formula (1):

(1)
（式中、Ｒ¹、Ｒ²、Ｒ³およびｎは上記のとおりである）
で表される化合物として得ることができる。

(1)
(Wherein R ¹ , R ² , R ³ and n are as described above)
It can obtain as a compound represented by these.

The raw material of the said reactive silyl group containing bisimide compound, a manufacturing method, etc. are demonstrated in detail.
<Allyl group-containing acid anhydride>
The following structural formula (3):

(3)
で表されるアリル基含有酸無水物において、アリル基は、上記式(3)中のシクロペンテン環骨格の炭素原子に結合した水素原子のいずれと置換されていてもよい。また、該アリル基含有酸無水物は、１種単独でも、前記アリル基の置換位置が異なる２種以上の異性体の組み合わせであっても差し支えない。

(3)
In the allyl group-containing acid anhydride represented by the formula (3), the allyl group may be substituted with any hydrogen atom bonded to the carbon atom of the cyclopentene ring skeleton in the above formula (3). The allyl group-containing acid anhydride may be a single type or a combination of two or more isomers having different substitution positions of the allyl group.

<Bifunctional diamine compound>
The following structural formula (4):
H ₂ N—R ¹ —NH ₂ (4)
(Wherein R ¹ is a divalent organic group)
In the bifunctional diamine compound represented by formula (1), the organic group may be a single type or a combination of two or more types.

R ¹ is preferably a divalent organic group having an aromatic ring or a linear organopolysiloxane structure, and specific examples of the organic group are shown below, but are not limited thereto.

（式中、ｐは０〜200の整数である）

(Wherein p is an integer from 0 to 200)

Other diamine compounds include p-phenylenediamine, 4,4′-diaminodiphenyl ether, 2,2′-bis (4-aminophenyl) propane, 4,4′-diaminodiphenyl sulfone, 4'-diaminodiphenyl sulfide, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (p-aminophenylsulfonyl) benzene, 1,4 -Bis (m-aminophenylsulfonyl) benzene, 1,4-bis (p-aminophenylthio) benzene, 1,4-bis (m-aminophenylthio) benzene, 2,2-bis [4- (4- Aminophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-chloro-4- (4-aminophenoxy) phenyl] propane 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-methyl-4- (4-aminophenoxy) phenyl] ethane 1,1-bis [3-chloro-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] ethane, bis [4- (4-aminophenoxy) phenyl] methane, bis [3-methyl-4- (4-aminophenoxy) phenyl] methane, bis [3-chloro-4- (4-aminophenoxy) phenyl] methane, bis [3, 5-dimethyl-4- (4-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] perfluoropropane And aromatic ring-containing diamines. These can be used singly or in combination of two or more.
Moreover, the diamine compound shown by following Structural formula (7) is also mentioned.

(7)

(7)

Here, in the above formula, R ⁴ represents one or more divalent groups selected from those exemplified in the above [Chemical Formula 20] to [Chemical Formula 24], or the “other diamine compound”. One or two or more divalent groups selected from the aromatic ring-containing organic group obtained by removing the amino group from the exemplified aromatic ring-containing diamine, q is an integer of 0 to 100, and X is an aromatic tetracarboxylic group It is a tetravalent organic group containing an aromatic ring derived from an acid dianhydride. The X may be a single type or a combination of two or more types.
Specific examples of X are shown below, but are not limited thereto.

更に、下記に示されるケイ素含有ジアミン類（例えば、ジアミノシロキサン、ジアミノシルエチレン、ジアミノシルフェニレン等）も使用することができる。

Furthermore, the following silicon-containing diamines (for example, diaminosiloxane, diaminosylethylene, diaminosylphenylene, etc.) can also be used.

なお、これらは１種単独でも２種以上を組み合わせても使用することができる。

These can be used singly or in combination of two or more.

  Among the above, the bifunctional diamine compound preferably used in the present invention is 4,4′-diaminodiphenylmethane and one or a combination of two or more of the following diamines.

<Preparation of allyl group-containing bisimide compound>
A polyamic acid is prepared from a tetracarboxylic acid and a diamine compound, and then the allylic group-containing acid anhydride and the bifunctional diamine compound are reacted in an organic solvent in the same manner as in a well-known synthetic method for obtaining a polyimide by ring closure. Let the following structural formula:

（式中、Ｒ¹は上記と同じである）
で表される中間体を得て、引き続き、この中間体を加熱条件下で脱水縮合して閉環させることにより、下記構造式(5)：

(Wherein R ¹ is the same as above)
Then, this intermediate is subjected to dehydration condensation under a heating condition and ring-closing, whereby the following structural formula (5):

(5)
で示されるアリル基含有ビスイミド化合物を得ることができる。

(Five)
The allyl group containing bisimide compound shown by these can be obtained.

<Preparation of reactive silyl group-containing bisimide compound>
The allyl group-containing bisimide compound and the following general formula (6):

(6)
（式中、Ｒ²、Ｒ³およびｎは上記のとおりである）
で表されるケイ素原子に結合した水素原子を１個有する有機シラン化合物とを、常法により、トルエン、メチルイソブチルケトン、テトラヒドロフラン等の溶媒中において、白金系触媒の存在下に反応させることにより、（アリル基中の）ビニル基（ＣＨ₂＝ＣＨ-）とケイ素原子に結合した水素原子（ＳｉＨ）とがヒドロシリル化反応により付加し、下記一般式(1)：

(6)
(Wherein R ² , R ³ and n are as described above)
By reacting an organic silane compound having one hydrogen atom bonded to a silicon atom represented by the following formula in a solvent such as toluene, methyl isobutyl ketone, tetrahydrofuran, etc. in the presence of a platinum-based catalyst, A vinyl group (in the allyl group) (CH ₂ ═CH—) and a hydrogen atom bonded to a silicon atom (SiH) are added by a hydrosilylation reaction, and the following general formula (1):

(1)
（式中、Ｒ¹、Ｒ²、Ｒ³およびｎは上記のとおりである）
で表される、本発明の(c)成分である反応性シリル基含有ビスイミド化合物を得ることができる。

(1)
(Wherein R ¹ , R ² , R ³ and n are as described above)
The reactive silyl group containing bisimide compound which is (c) component of this invention represented by these can be obtained.

Examples of R ² and R ³ in the organosilane compound represented by the general formula (6) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, Hexyl, heptyl, octyl, nonyl, decyl and other alkyl groups; cyclopentyl, cyclohexyl and other cycloalkyl groups; phenyl, tolyl, xylyl, naphthyl and other aryl groups; benzyl, phenethyl Groups, aralkyl groups such as phenylpropyl group; halogenated alkyl groups such as chloromethyl, 3-chloropropyl group, 3-fluorochloropropyl group, 3,3,3-trifluoropropyl group; vinyl group, allyl group, butenyl Group, propenyl group, isopropenyl group, butenyl group, pentenyl group, alkenyl group such as hexenyl group, etc. However, those having no aliphatic unsaturated bond are preferred, alkyl groups are more preferred, and methyl groups and ethyl groups are particularly preferred.

  Specific examples of the organosilane compound include the following compounds, but are not limited thereto.

上記の中でも、好適に使用される有機シラン化合物は、トリメトキシシラン：ＨＳi(ＯＣＨ₃)₃ である。
なお、上記有機シラン化合物は、１種単独でも２種以上を組み合わせても使用することができる。

Among the above, the organosilane compound preferably used is trimethoxysilane: HSi (OCH ₃ ) ₃ .
In addition, the said organosilane compound can be used even if single 1 type also combines 2 or more types.

The hydrosilylation reaction itself is well known in the art, and the amount of platinum catalyst used, reaction conditions, etc. may be as usual.
Specific examples of the component (c) include the following compounds.

In the hydrosilylation reaction, a hydrogen atom (SiH) bonded to a silicon atom is added exclusively to a vinyl group (CH ₂ ═CH—) (in an allyl group), but a cyclopentene ring in an allyl group-containing bisimide compound. Some addition reactions may also occur with respect to the carbon-carbon double bond (—CH═CH—). Even if the reactive silyl group-containing bisimide compound as the component (c) of the present invention contains an addition reaction product to the ring carbon-carbon double bond, the composition of the present invention is insulated as it is. Since it can be used as a protective film forming agent or the like, there is no problem.

The component (c) of the present invention can be used alone or in combination of two or more.
As the component (c) of the present invention, the following compounds are preferably used from the viewpoint of good adhesion after moisture absorption, electrode protection performance, and room temperature curability (or low temperature curability). .

  The amount of component (c) used is usually 5 to 200 parts by weight, preferably about 10 to 100 parts by weight, per 100 parts by weight of component (a). If the amount used is too small, the adhesion of the film obtained from the composition of the present invention to the substrate becomes insufficient, and it is not suitable as an electrode protective agent. On the other hand, if the amount is too large, the resulting coating becomes brittle, so it can be used for electrode protection on a hard substrate, but cannot be applied to electrode protection on a flexible substrate. .

[(D) Inorganic ion exchanger]
Examples of the inorganic ion exchanger used in the present invention include aluminosilicates such as natural zeolite and synthetic zeolite; metal oxides such as aluminum oxide and magnesium oxide; hydrous titanium oxide, hydrous bismuth oxide, hydrous antimony and the like. Hydroxides or hydrous oxides; acidic salts such as zirconium phosphate and titanium phosphate; basic salts such as hydrotalcites and complex hydrous oxides; heteropolyphosphoric acids such as ammonium molybdophosphate; or hexacyanoiron (III) A salt, hexacyano zinc, etc. are mentioned. Among these, since the chemical resistance is good and the impurity ion trap effect under wet conditions is good, hydroxides or hydrous oxides are good, and hydrous titanium oxide, hydrous bismuth hydrous, hydrous antimony hydrous, etc. preferable.

  The inorganic ion exchanger preferably has a cation exchange capacity of 0.1 meq / g or more in terms of Na ions and / or an anion exchange capacity of 0.1 meq / g or more in terms of Cl ions. If the ion exchange capacity is less than 0.1 meq / g, a large amount of addition is required, which is not preferable because the mechanical strength, flexibility, and the like of the film obtained by forming the composition are reduced. The various inorganic ion exchangers can be used alone or in combination of two or more.

  The amount of the inorganic ion exchanger used is in the range of 0.5 to 10 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polymer of component (a). If the amount used is too small, the impurity ion trapping effect is poor, and if it is too large, the mechanical properties of the film obtained by forming the composition will be reduced.

[Preparation of composition, etc.]
The synthesis of the polyimide silicone that is the polyamic acid of component (a) or a ring-closing derivative of the polyamic acid was charged into the reactor so that the diamine component and the tetracarboxylic acid component were substantially equimolar amounts, and heated in a solvent. To react. Preferably, the diamine component is dispersed or dissolved in the solvent in the reaction vessel, and the tetracarboxylic acid component is dissolved or dispersed in the solvent, and heated after dropwise stirring at a low temperature.

  As heating reaction temperature conditions, when obtaining a polyamic acid, it is 5-100 degreeC, Preferably it is the temperature within the range of 20-80 degreeC, and it is 1 to 100g of total amounts of a diamine component and a tetracarboxylic acid component. About 24 hours. Moreover, when obtaining the polyimide silicone substantially imidized completely, it is 120-200 degreeC, Preferably it is the temperature of the range of 140-180 degreeC, and it is 1 with respect to the total amount 100g of a diamine component and a tetracarboxylic acid component. What is necessary is just to heat for about 24 hours. Below 120 ° C, the conversion rate is slow and may be above 200 ° C, but there is no particular benefit.

The reactive silyl group-containing bisimide compound (c) and the inorganic ion exchanger (d) are combined after the heating reaction is completed.
As a preferred embodiment, in addition to the specific examples described below, the following general formula (2):
H ₂ N—Z— (SiR ₂ O) _m —SiR ₂ —Z—NH ₂ (2)
(In the formula, Z, R and m are as described above.)
A diamine component consisting of 10 to 15 mol% of diaminosiloxane and 85 to 90 mol% of bis [4- (4-aminophenoxy) phenyl] sulfone, 50 to 80 mol% of pyromellitic dianhydride and benzophenone tetra A tetracarboxylic acid component comprising 20 to 50 mol% of carboxylic dianhydride, in an amount equivalent to cyclohexanone, γ-butyrolactone or N-methylpyrrolidone in an amount equivalent to a resin solid content of 30 to 45 wt%. Reacting in a solvent to produce polyimide silicone substantially imidized, and after completion of the reaction, the reactive silyl group-containing bisimide compound of component (c) and inorganic ion exchange of component (d) It is to mix the body.

[Other ingredients]
In addition to the components (a) to (d) described above, it is optional to use other components in the composition of the present invention as long as the characteristics of the composition of the present invention are not impaired.
The reactive silyl group-containing bisimide compound which is the component (c) of the present invention has a condensation reactive group such as an alkoxy group or an alkenoxy group at both ends. For the purpose of accelerating curing, it is desirable to blend a conventionally known condensation reaction catalyst. Examples of the condensation reaction catalyst include titanium-containing organic compounds such as tetraisopropoxytitanium, tetrabutoxytitanium, titanium bisacetylacetonate, and titanium chelate compounds; tetramethylguanidine, tetramethylguanidylpropyltrimethoxysilane, and the like. Strong bases of: zinc octoate, lead 2-ethylhexanoate, dibutyltin diacetate, dibutyltin dilactate, dibutyltin dioctate, stannous octoate, zinc naphthenate, ferrous octoate And carboxylic acid metal salts such as These can be used singly or in combination of two or more. When this condensation reaction catalyst is used, its blending amount is not particularly limited as long as it is an effective amount as a catalyst, but is usually 0.01 to 6.0 parts by mass, preferably 100 parts by mass of component (c). Is about 0.05 to 5.0 parts by mass.

[Coating film]
The polyimide silicone resin composition of the present invention can be formed, crosslinked and cured by simply removing the solvent after coating on a substrate. The conditions for solvent removal vary depending on the coating film thickness, but are usually heated at 20 to 150 ° C for about 1 to 150 minutes using an oven, hot plate, etc. in an inert atmosphere such as air or nitrogen. Do. The temperature condition may be constant over the entire processing time, or may be performed while gradually raising the temperature within the temperature range.

  In addition, when the component (a) is a polyamic acid or is a polyimide silicone that is insufficiently imidized, the polyimide silicone is substantially completely imidized by a ring-closing reaction by firing after film formation. And The firing conditions vary depending on the film thickness, but using an oven, a hot plate or the like, the temperature is usually in the temperature range of 150 to 400 ° C. for 10 minutes to 5 hours, preferably about 20 minutes to 3 hours.

Note that the reactive silyl group-containing bisimide compound (c) is crosslinked and cured by a condensation reaction between the components under the conditions in the solvent removal and film-forming steps, and further under the firing conditions.
The film thickness of the polyimide silicone coating thus obtained is usually 5 to 250 μm, preferably 5 to 200 μm, and more preferably 10 to 100 μm.

  Although it does not specifically limit as a base material, For example, organic base materials which consist of a polyimide, BT resin, etc .; Metals, such as aluminum, copper, silicon, or these alloys, or stainless steel; Alumina, glass, borosilicate glass, quartz, zirconia And ceramic materials such as mullite and silicon nitride; and semiconductor materials such as barium titanate, lithium niobate, tantalum niobate, gallium arsenide, and indium phosphorus. Moreover, on the surface of these base materials, high heat resistance such as polyimide, aromatic polyamide, polyphenylene, polyxylylene, polyphenylene oxide, polysulfone, polyamideimide, polyesterimide, polybenzimidazole, polyquinazolinedione, polybenzoxazinone, etc. You may coat the polyimide silicone resin composition of this invention with respect to the base material which coat | covered the molecular compound.

[Viscosity of resin composition]
The viscosity of the resin composition of the present invention is preferably 10 to 2000 mPa · s, particularly preferably 100 to 800 mPa · s at 25 ° C., according to the Brookfield viscosity measurement method described later. When the viscosity is too high, the narrow gap penetration property is lowered, and when the viscosity is too low, the desired film thickness cannot be obtained, and the electrode is likely to be corroded or disconnected.

[Usage]
Specific application examples of the polyimide silicone resin composition of the present invention include monolithic ICs on a substrate made of silicon wafer, gallium arsenide, etc., such as DRAM, SRAM, CPU, etc .; ceramic substrates, glass substrates, etc. Devices such as hybrid ICs, thermal heads, image sensors, and multi-chip high-density mounting boards formed on them; interlayer insulation films such as TAB tape, flexible substrates, and various wiring boards such as rigid wiring boards, surface protective films, α Application to protective films having various purposes such as line shielding can be given.

  Synthesis Examples, Examples and Comparative Examples are shown below to describe the present invention in more detail, but the present invention is not limited to these.

[Synthesis Example 1]
In a glass four-necked separable flask equipped with a thermocouple, stirrer, and reflux condenser, 3,3 ', 4,4'-diphenylsulfonetetra so that the diamine component and tetracarboxylic acid component are equimolar. Carboxylic dianhydride (DSDA) 19.45 g (mol% when the total of parts by mass of the tetracarboxylic acid component and the diamine component is 100 mol%: 25 mol% (the same applies to “mol%” described below) )), 3,3 ′, 4,4 ′-(2,2-diphenylhexafluoropropane) tetracarboxylic dianhydride (6FDA) 24.11 g (25 mol%), the following formula (8):
H ₂ N-CH ₂ CH ₂ CH _2- [Si (CH ₃ ) ₂ O] ₉ -Si (CH ₃ ) ₂ -CH ₂ CH ₂ CH ₂ -NH ₂ (8)
Diaminopolysiloxane (KF-8010 (trade name), manufactured by Shin-Etsu Chemical Co., Ltd.) 36.55 g (20 mol%), 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) 13.37 g (15 mol%) and 4,4'-diaminodiphenyl ether (ODA) 6.52 g (15 mol%) were charged, 300 g cyclohexanone was added, and the mixture was stirred at 180 ° C. for 4 hours. A composition was obtained.

[Synthesis Example 2-5]
Synthetic Example 1 except that the composition and the amount (parts by mass) of the diamine component and tetracarboxylic acid component described in Synthetic Example 1 are changed as shown in Table 1 (mol% is shown in parentheses). In the same manner as above, a composition comprising polyimide silicone and a solvent was obtained.

[Synthesis Example 6]
(1) In a flask equipped with a stirrer, a thermometer and a nitrogen displacement device, 24.85 g (0.1 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane and N-methyl-2-pyrrolidone as a solvent Charge 80 g and 100 g of cyclohexanone and stir while stirring allyl nadic acid anhydride (the following structural formula:

で表される化合物と、下記構造式：

And the following structural formula:

で表される化合物とを、合計で約80モル％含有する異性体混合物）（商品名：ＡＮＡＨ、丸善石油化学社製）40.8ｇ(0.2モル)を徐々に滴下した。滴下終了後、更に室温で 10時間撹拌し、次に、前記フラスコに水分受容器付き還流冷却器を取り付けた後、キシレン 30ｇを加え、反応系を 160℃に昇温して、その温度を２時間保持した。更に、温度を 175℃まで昇温させて、その温度を４時間保持した。この反応によって生成した水分の量は 3.5ｇであった。

40.8 g (0.2 mol) of an isomer mixture containing about 80 mol% in total (trade name: ANAH, manufactured by Maruzen Petrochemical Co., Ltd.) was gradually added dropwise. After completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Next, a reflux condenser with a moisture receiver was attached to the flask, 30 g of xylene was added, the reaction system was heated to 160 ° C., and the temperature was increased to 2 Held for hours. Further, the temperature was raised to 175 ° C., and the temperature was maintained for 4 hours. The amount of water produced by this reaction was 3.5 g.

  The reddish brown reaction solution obtained by the above operation was cooled to room temperature and then stripped under reduced pressure to remove the solvent.

  Next, after adding 600 g of methyl isobutyl ketone to the obtained reaction product and dissolving, water (600 ml) was added, stirred and washed with water. Thereafter, the aqueous phase was separated and the electrical conductivity of the aqueous phase was measured. The washing operation was repeated until the conductivity of the water phase after washing was 10 μS / cm or less. Thereafter, water is removed from the methyl isobutyl ketone solution by azeotropic dehydration, and the obtained reaction solution is poured into methanol to precipitate a solid product. Then, the solvent is removed, and a bisimide compound having the following structural formula ( BI-1) 59g was obtained.

When an infrared absorption spectrum of the bisimide compound (BI-1) was observed, absorption derived from an imide bond was observed at 1768 cm ⁻¹ and absorption derived from a vinyl group was observed at 1641 cm ⁻¹ . Further, from the NMR spectrum, a peak derived from a vinyl group was observed at 5.0 ppm.

(2) 59 g (0.095 mol) of the bisimide compound (BI-1) was dissolved again in 600 g of methyl isobutyl ketone, and the temperature was raised to perform azeotropic dehydration. To this solution was added 0.2 g of chloroplatinic acid, and 26 g (0.22 mol) of trimethoxysilane was added dropwise at the reflux temperature. After stirring for 6 hours at the reflux temperature, excess trimethoxysilane was removed from the resulting reaction solution by atmospheric distillation to obtain 164.4 g of a reaction product solution (non-volatile content: 50%). From this, the solvent was removed to obtain 82.2 g of a methoxysilyl group-containing bisimide compound (BI-1MS) having the following structural formula.

When the infrared absorption spectrum of this methoxysilyl group-containing bisimide compound (BI-1MS) was observed, the absorption derived from the SiO bond was observed at 1086 cm ⁻¹ and the absorption derived from the allyl group (1641 cm ⁻¹ ) disappeared. It was observed that It was also observed from the NMR spectrum that the peak derived from the allyl group (5.0 ppm) had disappeared.

[Synthesis Example 7]
(1) In place of 1,3-bis (3-aminopropyl) tetramethyldisiloxane described in Synthesis Example 6 (1), except that 19.83 g (0.1 mol) of 4,4′-diaminodiphenylmethane is used, In the same manner as in Synthesis Example 6, 48.5 g of a bisimide compound (BI-2) having the following structural formula was obtained.

  When the infrared absorption spectrum and NMR spectrum of this bisimide compound (BI-2) were observed, they were the same as the observation results described in Synthesis Example 6.

(2) Instead of 59 g (0.095 mol) of the bisimide compound (BI-1) described in Synthesis Example 6 (2), 48.5 g (0.085 mol) of the bisimide compound (BI-2) is used, and trimethoxysilane 69.2 g (0.085 mol) of a methoxysilyl group-containing bisimide compound (BI-2MS) having the following structural formula was obtained in the same manner as in Synthesis Example 6 except that 24.9 g (0.20 mol) was used.

  When an infrared absorption spectrum and an NMR spectrum of this methoxysilyl group-containing bisimide compound (BI-2MS) were observed, the results were the same as those described in Synthesis Example 6.

[Synthesis Example 8]
(1) Instead of 1,3-bis (3-aminopropyl) tetramethyldisiloxane described in Synthesis Example 6 (1), a diamine compound represented by the following structural formula:

31.0ｇ（0.1モル）を用いること以外は、合成例６と同じにして、下記構造式を有するビスイミド化合物（BI-3）56.6ｇを得た。

56.6 g of bisimide compound (BI-3) having the following structural formula was obtained in the same manner as in Synthesis Example 6 except that 31.0 g (0.1 mol) was used.

  When an infrared absorption spectrum and an NMR spectrum of the bisimide compound (BI-3) were observed, the results were the same as those described in Synthesis Example 6.

(2) Instead of 59 g (0.095 mol) of the bisimide compound (BI-1) described in Synthesis Example 6 (2), 56.6 g (0.083 mol) of the bisimide compound (BI-3) is used, and trimethoxysilane In the same manner as in Synthesis Example 6 except that 24 g (0.2 mol) was used, 76.8 g (0.083 mol) of a methoxysilyl group-containing bisimide compound (BI-3MS) having the following structural formula was obtained.

  When an infrared absorption spectrum and an NMR spectrum of this methoxysilyl group-containing bisimide compound (BI-3MS) were observed, the results were the same as those described in Synthesis Example 6.

<Examples 1 to 10>
Compositions comprising the polyimide silicones and solvents obtained in Synthesis Examples 1-5, methoxysilyl group-containing bisimide compounds (BI-1MS-BI-3MS) obtained in Synthesis Examples 6-8, and condensation reaction catalysts Tetraisopropyl titanate: Ti (O—iPr) ₄ and the inorganic ion exchanger were mixed in the compositions and amounts used (parts by mass) described in Table 2, Table 3 and Table 4, and then sufficiently stirred, A polyimide silicone resin composition of the present invention was prepared.

  As an inorganic ion exchanger, “IXE633” (trade name, manufactured by Toa Gosei Co., Ltd.) (hydrous hydrous antimony / hydrous hydrous bismuth mixture, [ion exchange capacity] cation: 1.1 meq / g, anion: 1.4 meq / g), “IXE600” (trade name, manufactured by Toa Gosei Co., Ltd.) (hydrous hydrous antimony / hydrous hydrous bismuth mixture, [ion exchange capacity] cation: 1.5 meq / g, anion: 2.0 meq / g), or “Kyoward 2200” (Trade name, manufactured by Kyowa Chemical Industry Co., Ltd.) (magnesium oxide / aluminum oxide mixture, [ion exchange capacity] anion: 6.7 meq / g) (hereinafter abbreviated as “KW2200”) was used.

  Subsequently, the performance evaluation test was performed as follows about each polyimide silicone resin composition of Examples 1-10.

[Adhesive strength measurement]
Apply a polyimide silicone resin composition on a glass plate, leave it for 72 hours at 23 ° C and 60% humidity, and evaporate the solvent to remove it. 10mm x 150mm and a film thickness of 50μm on average A film was prepared.

  One end of the film in the longitudinal direction was pulled in a direction parallel to the glass plate and at an angle of 180 ° at a speed of 300 mm / min, and peel peel strength (g / cm) was measured. The measurement results are shown in the column of “Adhesive strength” in Tables 2 and 3.

[Constant voltage applied ITO electrode corrosion test]
An ITO comb electrode having an area of 10 mm × 5 mm was produced between a line width of 15 μm and a line of 15 μm. On this electrode surface, a polyimide silicone resin composition was applied, and allowed to stand for 72 hours at 23 ° C. and 60% humidity to form a coating having an average thickness of 50 μm.

  The obtained ITO comb electrode was subjected to a continuity test under conditions of applying a constant voltage of 85 ° C., humidity 85%, and 20V. The time (hrs) until corrosion of the ITO electrode occurred was measured by microscopic observation. The measurement results are shown in the column of “Electrode Corrosion Test” in Tables 2 and 3.

[Viscosity measurement]
The viscosity (mPa · s) at 25 ° C. of the polyimide silicone resin composition was measured with a DVIII viscometer (manufactured by Brookfield) using a cone in the corresponding viscosity range.

[Narrow gap penetration measurement]
ACF of 5 mm × 10 mm (CP9630SB (manufactured by Sony Chemical)) is pasted on a glass substrate with a die bonder (manufactured by Athlete) at 200 ° C. for 10 seconds at 10 MPa. The ACF-attached glass substrate is observed from the back side, and a micrograph of the holes existing on the ACF and glass bonding surface is taken. On a glass substrate with ACF, 0.2 mL of polyimide silicone resin composition (impregnating agent) is applied around ACF so as to draw a rectangle of 5 mm × 10 mm and dried for one day. The glass substrate coated with the impregnating agent is again observed from the back surface to obtain a micrograph. The area ratio (%) between the impregnating agent and the air layer existing at the interface between the ACF and the glass is calculated from the photograph to make the narrow gap penetration property.

[Comparative Example 1]
Except not using a reactive silyl group containing bisimide compound, it carried out similarly to Example 1, and prepared the polyimide silicone type resin composition, film formation, etc., and the said performance evaluation test. The results are shown in Table 5. (The ITO electrode was corroded in less than 168 hours, causing a disconnection.)

[Comparative Examples 2 to 5]
Do not use reactive silyl group-containing bisimide compounds, mercapto group-containing alkoxysilane hydrolysis condensate: KBM-803P (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) or hydrosilyl group-containing alkoxysilane: 03MS (trade name, Shin-Etsu Chemical) The same as in Example 1, except that tetraisopropyl titanate is used in the composition and use amount (parts by mass) described in Table 5, and the preparation of the polyimide silicone resin composition, film formation, etc. A performance evaluation test was conducted. The results are shown in Table 5.

[Comparative Example 6]
Except not using an inorganic ion exchanger, it carried out similarly to Example 1, and prepared the polyimide silicone resin composition, film formation, etc., and the said performance evaluation test. The results are shown in Table 6.

[Comparative Examples 7 and 8]
Except that the amount of the inorganic ion exchanger was outside the range of the composition of the present application, the preparation of the polyimide silicone resin composition, film formation, and the performance evaluation test were performed in the same manner as in Example 1. The results are shown in Table 6.

Claims (6)

(a) a polyamic acid which is a reaction product of a tetracarboxylic acid compound selected from the group consisting of an aromatic tetracarboxylic acid compound and an alicyclic tetracarboxylic acid compound, an aromatic diamine and a diaminosiloxane, and the polyamic acid A polymer selected from the group consisting of polyimide silicones which are ring-closing derivatives,
(b) N-methylpyrrolidone, amide solvents, lactones, carbonates, esters, ethers, ketones, alcohols, urea solvents, sulfoxide solvents, sulfone solvents, hydrocarbon solvents, and halogen solvents One or more solvents selected from the group consisting of solvents,
(c) Structural formula (1) below:

(1)
(Wherein R ¹ is a divalent organic group having an aromatic ring or a linear organopolysiloxane structure , and R ² and R ³ are independently unsubstituted or substituted monovalent carbon atoms having 1 to 10 carbon atoms. A hydrogen group and n is an integer of 1 to 3 independently)
A reactive silyl group-containing bisimide compound represented by:
(d) Inorganic ion exchanger: (a) A polyimide silicone resin composition containing 0.5 to 10 parts by mass with respect to 100 parts by mass of the component.   The cation exchange capacity of the (d) inorganic ion exchanger is 0.1 meq / g or more in terms of Na ions, and / or the anion exchange capacity is 0.1 meq / g or more in terms of Cl ions. A composition according to 1.   The composition according to claim 1 or 2, which has a viscosity at 25 ° C of 10 to 2,000 mPa · s. In the component (b),
The amide solvent is one or two solvents selected from the group consisting of N, N-dimethylformamide and N, N-dimethylacetamide;
The lactone is one or more solvents selected from the group consisting of γ-butyrolactone, α-methyl-γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone. ,
The carbonates are propylene carbonate,
The ester is one or more solvents selected from the group consisting of butyl acetate, ethyl cellosolve acetate, and butyl cellosolve acetate,
The ethers are one or more solvents selected from the group consisting of dibutyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetrahydrofuran;
The ketones are one or more solvents selected from the group consisting of methyl isobutyl ketone, cyclohexanone, and acetophenone;
The alcohol is one or more solvents selected from the group consisting of butanol, octanol, and ethyl cellosolve;
The sulfoxide solvent is dimethyl sulfoxide;
The hydrocarbon solvent is toluene;
The halogen solvent is one or two solvents selected from the group consisting of chloroform and carbon tetrachloride.
The composition according to any one of claims 1 to 3. R ¹ But

(Wherein p is an integer from 0 to 200);

p-phenylenediamine, 4,4′-diaminodiphenyl ether, 2,2′-bis (4-aminophenyl) propane, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, 1, 4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (p-aminophenylsulfonyl) benzene, 1,4-bis (m-aminophenylsulfonyl) Benzene, 1,4-bis (p-aminophenylthio) benzene, 1,4-bis (m-aminophenylthio) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2, 2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-chloro-4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-methyl-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-chloro-4- (4-aminophenoxy) ) Phenyl] ethane, 1,1-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] ethane, bis [4- (4-aminophenoxy) phenyl] methane, bis [3-methyl-4 -(4-Aminophenoxy) phenyl] methane, bis [3-chloro-4- (4-aminophenoxy) phenyl] methane, bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] methane, bis One or more aromatic ring-containing diamines selected from the group consisting of [4- (4-aminophenoxy) phenyl] sulfone and 2,2-bis [4- (4-aminophenoxy) phenyl] perfluoropropane A residue obtained by removing an amino group from
The following structural formula (7):

(7)
(Wherein R ^Four Is

Wherein p is as described above;

P-phenylenediamine, 4,4′-diaminodiphenyl ether, 2,2′-bis (4-aminophenyl) propane, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (p-aminophenylsulfonyl) benzene, 1,4-bis (m-aminophenyl) Sulfonyl) benzene, 1,4-bis (p-aminophenylthio) benzene, 1,4-bis (m-aminophenylthio) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-chloro-4- (4-aminophenoxy) phenyl] propane, 1,1-bis [ 4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-methyl-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-chloro-4- (4-amino) Phenoxy) phenyl] ethane, 1,1-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] ethane, bis [4- (4-aminophenoxy) phenyl] methane, bis [3-methyl- 4- (4-aminophenoxy) phenyl] methane, bis [3-chloro-4- (4-aminophenoxy) phenyl] methane, bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] methane, One or more aromatic rings selected from the group consisting of bis [4- (4-aminophenoxy) phenyl] sulfone and 2,2-bis [4- (4-aminophenoxy) phenyl] perfluoropropane Residue obtained by removing amino group from diamine
One or two or more divalent groups selected from the group consisting of: q is an integer of 0 to 100, and X is a tetravalent group containing an aromatic ring derived from an aromatic tetracarboxylic dianhydride. Organic group. )
A residue obtained by removing an amino group from the diamine compound represented by:

Residues obtained by removing amino groups from one or more silicon-containing diamines selected from the group consisting of
The composition according to any one of claims 1 to 4, which is one or more divalent organic groups selected from the group consisting of: The electrode protective material which consists of a composition of any one of Claims 1-5 .