JP3134488B2 - Siloxane-polyimide cocondensate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silicon-modified polyimide, a precursor solution thereof, and a method for producing the precursor solution.
More specifically, it is tough, excellent in heat resistance, improved brittleness which is a drawback of inorganic compounds, siloxane-polyimide cocondensate whose hardness was controlled, its precursor solution excellent in coatability, and precursor solution A method for producing the same.

[0002]

2. Description of the Related Art A silica-based coating solution (so-called SOG), which is a solution obtained by hydrolyzing and polycondensing an alkoxysilane, is widely used as a coating agent for electronic materials. The viscosity of this coating liquid is as low as several centipoise, so it is excellent in coatability, such as filling in fine patterns, and by baking, the resulting silicon oxide coating has high hardness and excellent flatness. However, it has the drawback that it is brittle, cracks easily occur, and a thick film cannot be obtained. On the other hand, the viscosity of a polyimide-based coating solution is usually
Since it is as high as 100 to several thousand centipoise, it is inferior in coatability such as filling of fine pattern holes. The coating film is also inferior to inorganic materials in terms of heat resistance and hardness. A coating solution in which a polyimide (usually a precursor thereof) and a hydrolyzed polycondensate of an alkoxysilane are mixed (a reaction is also performed after a part of the mixture) has already been proposed (for example, Japanese Patent Application Laid-Open No. JP-A-99234, JP-A-63-99235, JP-A-63-172741, JP-A-63-1
93935, JP-A-63-199265,
JP-A-63-291924, JP-A-2-2029
No. 50, JP-A-3-287626). However, due to the hydrolysis of alkoxysilane, unreacted substances of the added water remain in the coating solution, and this water causes hydrolysis of the polyimide precursor (usually polyamic acid), As a result, there is a disadvantage that the viscosity of the coating liquid changes greatly with time. To avoid this, unreacted water must be removed by adding a step such as solvent replacement.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art. That is,
An object of the present invention is to provide a mixed solution of a polyimide precursor and an alkoxysilane polycondensate, which has little change over time in viscosity, is excellent in storage stability, and is excellent in coating properties. Furthermore, it has excellent heat resistance,
An object of the present invention is to provide a siloxane-polyimide cocondensate having a controlled hardness.

[0004]

Means for Solving the Problems The present inventors have conducted various studies in order to solve the above-mentioned problems relating to the known art. As a result, even in a non-aqueous solution, it has been found that a mixed solution of a polyimide precursor and an alkoxysilane polycondensate can be obtained in a one-step reaction, and a coating solution in which the above-described problems have been solved is obtained. It was found that the siloxane-polyimide co-condensate obtained by firing also had excellent physical properties, and the present invention was completed.

The present invention provides the following (1), (2) and (3)
It has a configuration of (1) After reacting a tetracarboxylic dianhydride represented by the following general formula (I) with a silane represented by the following general formula (II) in an organic solvent, the solution is added to the solution by the following general formula (III) The siloxane-polyimide precursor solution obtained by adding at least one of the diamine shown and the aminosilane represented by the following general formula (IV) and reacting at a temperature lower than 150 ° C. to a temperature of 150 to 500 ° C. By heating, the solvent is volatilized, an imidization reaction and a siloxane condensation reaction are performed, and a cured siloxane-polyimide cocondensate obtained as a result.

[0006]

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Embedded image ｛Wherein, in the general formulas (I), (II), (III) and (IV), R ¹ is tetravalent, R ² and R ³ are divalent,
R ⁴ , R ⁵ , R ⁶ and R ⁷ represent a monovalent organic group, and m and n are 1 <m, n ≦ 4.

(2) After reacting the tetracarboxylic dianhydride represented by the general formula (I) with the alkoxysilane represented by the general formula (II) in an organic solvent, the solution is added to the solution represented by the general formula (I). A siloxane-polyimide precursor solution obtained by adding and reacting at least one of a diamine represented by (III) and an aminosilane represented by the general formula (IV).

(3) After reacting the tetracarboxylic dianhydride represented by the general formula (I) with the alkoxysilane represented by the general formula (II) in an organic solvent, A method for producing a siloxane-polyimide precursor solution, comprising adding one or more of a diamine represented by the formula (III) and an aminosilane represented by the general formula (IV) and reacting at a temperature of less than 150 ° C. Law.

Hereinafter, the structure and effect of the present invention will be described in detail. The siloxane-polyimide precursor solution is prepared by reacting a tetracarboxylic dianhydride represented by the general formula (I) with an alkoxysilane represented by the general formula (II), and a reaction product thereof with the general formulas (III) and (III). It is synthesized by a two-stage reaction of reacting with one or more amino compounds represented by IV). The obtained siloxane-polyimide precursor solution is applied to a substrate or the like and baked to obtain a siloxane-polyimide cocondensate.

Specific examples of the tetracarboxylic dianhydride used in the present invention include, but are not necessarily limited to, the following compounds. Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-bifulvic dianhydride 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenonetetraanhydride Carboxylic dianhydride, 2,3,3 ', 4'
-Benzophenonetetracarboxylic dianhydride, bis-
(3,4-dicarboxyphenyl) ether dianhydride,
Bis- (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2, Examples of alicyclic tetracarboxylic dianhydrides such as 2-bis- (3,4-dicarboxyphenyl) hexafluoropropane dianhydride include cyclobutanetetracarboxylic dianhydride and methylcyclobutanetetracarboxylic dianhydride. Examples of the aliphatic tetracarboxylic dianhydride include known compounds such as 1,2,3,4-tetracarboxybutane dianhydride.

In the alkoxysilane represented by the general formula (II), R ₆ is preferably an alkyl group having 1 to ₆ carbon atoms, a phenyl group, a 7 to 12 alkyl-substituted phenyl group or the like. In the present invention, it is possible to use two or more kinds of alkoxysilanes, but their mixing ratio is 1
<M ≦ 4.

The following compounds can be mentioned as specific examples of the alkoxysilane used in the present invention, but are not necessarily limited thereto. Tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane , Phenyltripropoxysilane, phenyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, methylethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldipropoxysilane, Diphenyldibutoxysilane, methylphenyldiethoxysilane, trimethylethoxysilane, triphenylethoxysilane Any known compounds may be mentioned.

In the present invention, the following compounds can be mentioned as specific examples of preferred solvents (hereinafter, sometimes referred to as reaction solvents) for reacting the above-mentioned starting compounds in a solvent. N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, pyridine, hexamethylphosphoramide, methylformamide, N-
Acetyl-2-pyrrolidone, 2-methoxyethanol,
2-ethoxyethanol, 2-butoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, cyclopentanone, methylcyclopentanone, cyclohexanone, cresol, γ-butyrolactone, isophorone, N, N-diethylacetamide , N, N-diethylformamide, N, N-dimethylmethoxyacetamide, tetrahydrofuran, N-methyl-ε-caprolactam, tetrahydrathiophene dioxide {sulfolane}. Methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, t-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol and the like. This reaction also involves the conversion of the organic solvent into another aprotic (neutral) organic solvent, such as aromatic, alicyclic or aliphatic hydrocarbons, or their chlorinated derivatives (eg, benzene, toluene, xylenes). , Cyclohexane, pentane, hexane, petroleum ether, methylene chloride) or dioxane.

The reaction between the tetracarboxylic dianhydride and the alkoxysilane is carried out in an organic solvent at 20 to 100 ° C., preferably 30 to 70 ° C. for 1 to 30 hours. As an example of the reaction at this time, the following formula (V) is used for the reaction between one molecule of tetracarboxylic dianhydride and two molecules of alkoxysilane.
Is shown.

[0015]

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In this reaction, if the ratio of alkoxysilane to tetracarboxylic dianhydride is small, a single molecule adduct may be obtained in some cases. In this way, one of the alkoxysilanes is added to the tetracarboxylic dianhydride.
A molecular or bimolecular adduct is obtained. The mixing ratio between tetracarboxylic dianhydride and alkoxysilane does not need to be particularly limited, but if the former ratio is increased, the obtained siloxane-polyimide cocondensate has a stronger polyimide property, and conversely the alkoxysilane When the ratio is increased, the characteristics of the siloxane become stronger. In order to make both characteristics obvious, the ratio of the alkoxysilane to the tetracarboxylic dianhydride is preferably 0.01 to 100 (molar ratio).

The following compounds can be mentioned as amino compounds which react with the reaction product of tetracarboxylic dianhydride and alkoxysilane.

The following compounds can be mentioned as specific examples of the diamine used in the present invention, but are not necessarily limited thereto. As the aromatic diamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone,
4,4'-diaminodiphenyl sulfide, 4,4'-
Di (methaminophenoxy) diphenyl sulfone, 4,
4'-di (paraaminophenoxy) diphenylsulfone, orthophenylenediamine, metaphenylenediamine, paraphenylenediamine, benzidine, 3,3'-
Diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl-2,2-propane, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 4,4'-bis (4-aminophenoxy )
Biphenyl, 2,2-bis {4- (4-aminophenoxy) phenyl} hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4
-Aminophenoxy) benzene, 4,4'-diamino-
3,3′-diethyl-5,5′-dimethyldiphenylmethane, 4,4′-diamino-3,3 ′, 5,5′-tetramethyldiphenylmethane, 1,4-diaminotoluene, metaxylylenediamine, 2, Aliphatic diamines such as 2'-dimethylbenzidine and the like are aliphatic diamines such as trimethylenediamine, tetramethylenediamine, hexamethylenediamine and 2,11-dodecanediamine, and silicon-based diamines are bis (paraaminophenoxy) dimethylsilane and 1,4-bis Examples of alicyclic diamines such as (3-aminopropyldimethylsilyl) benzene and the like include 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane and isophoronediamine, and examples of guanamines include acetoguanamine and benzoguanamine. Can be. Examples of the diaminosiloxane include compounds represented by the following formula (where p is 1 to 100). Known diamines other than those shown above can also be used.

The following compounds can be mentioned as specific examples of the aminosilane used in the present invention, but are not necessarily limited thereto. Aminomethyl-di-n
-Propoxy-methylsilane, (β-aminoethyl)-
n-propoxy-methylsilane, (β-aminoethyl)
-Diethoxy-phenylsilane, (β-aminoethyl)
-Tri-n-propoxysilane, (β-aminoethyl)
-Dimethoxy-methylsilane, (γ-aminopropyl)
-Di-n-propoxy-methylsilane, (γ-aminopropyl) -di-n-butoxy-methylsilane, (γ-aminopropyl) -triethoxysilane, (γ-aminopropyl) -di-n-pentoxy-phenylsilane , (Γ
-Aminopropyl) -methoxy-n-propoxy-methylsilane, (δ-aminobutyl) -dimethoxy-methylsilane, (3-aminophenyl) -di-n-propoxysilane, (4-aminophenyl) -tri-n-propoxy Silane, {β- (4-aminophenyl) ethyl} -diethoxy-methylsilane, {β- (3-aminophenyl) ethyl} -di-n-propoxy-phenylsilane,
{Γ- (4-aminophenyl) propyl} -di-n-propoxy-methylsilane, {γ- (4-aminophenoxy) propyl} -di-n-propoxy-methylsilane,
{Γ- (3-aminophenoxy) propyl} -di-n-
Butoxy-methylsilane, {γ- (3-aminophenoxy) propyl} -dimethyl-methoxysilane, (γ-aminopropyl) -methyl-diethoxysilane, (γ-aminopropyl) ethyl-di-n-propoxysilane,
(4-aminophenyl) -trimethoxysilane, (3-
(Aminophenyl) -trimethoxysilane, (4-aminophenyl) -methyl-dimethoxy-silane, (3-aminophenyl) -dimethyl-methoxysilane, (4-aminophenyl) -triethoxysilane, {3- (triethoxy) Known compounds such as silyl) propyl diurea can be mentioned.

The reaction of an adduct of tetracarboxylic dianhydride with an alkoxysilane and an amino compound such as a diamine represented by the general formula (III) is represented by the following formula (VI)

[0021]

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As shown in the above, a polyamic acid ester and hydroxy lan are formed. If the reaction product of tetracarboxylic dianhydride and alkoxysilane contains partially unreacted tetracarboxylic dianhydride, the product of this reaction is a polymer composed of amic acid and amic acid ester. And hydroxysilane. If the amino compound is an aminosilane represented by the general formula (IV), the product of this reaction consists of an amic acid ester and a hydroxysilane. Further, when the amino compound is a mixture of a diamine and an aminosilane, the reaction product has an aminosilane added to the terminal (with amic acid).
It consists of a polymer consisting of an amic acid ester and hydroxysilane. The hydroxy group of the hydroxysilane formed by the above-described reaction is highly reactive with other hydroxy groups or alkoxy groups, and polymerizes while generating water or alcohol. In addition, the generated water reacts with the alkoxy group to generate alcohol and hydroxysilane. That is, the following reaction (shown in equation (VII))

[0023]

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By repeating this, a siloxane polymerized is formed. The hydroxyl group not only reacts with the alkoxy group of the unreacted alkoxysilane, but also (amidic acid)
It reacts with the alkoxy group of aminosilane present at the terminal of the amic acid ester polymer, and is incorporated into the polymer.

This step comprises a reaction of a carboxylic anhydride with an alkoxysilane and an amine, a reaction of a carboxylic anhydride with an amine, and a siloxane condensation reaction. Preferred conditions for these reactions are as follows: 0-150
° C, particularly preferably 20 to 70 ° C, and the time is 0.5 to
100 hours, particularly preferably about 3 to 30 hours. Thus, the siloxane-polyimide precursor solution of the present invention can be obtained.

The siloxane-polyimide precursor solution of the present invention can be used as it is because it is obtained in a state of being dissolved in a solvent. The reaction solution is preferably used as it is, or after being concentrated or diluted with a solvent. As the diluting solvent, the same solvent as the reaction solvent can be used.
As a method for curing the siloxane-polyimide precursor solution by heating, any known method may be used. For example, after applying the siloxane-polyimide precursor solution of the present invention on a substrate such as a glass plate, a copper plate, an aluminum plate, or a silicon wafer, 150 to 50
By baking at a temperature of 0 ° C., the siloxane-polyimide cocondensate of the present invention can be obtained. The coating method may be any method, but is usually selected from a spin coating method, a printing method, a dipping method and a roll coater method.

The siloxane-polyimide cocondensate of the present invention is used for various protective films for semiconductors, flattening films, insulating films, alignment films for liquid crystals, base materials for color filters, protective films for thermal heads, Various electronic parts such as parts, films, molding materials, and the like are conceivable.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

The measurement in the examples and comparative examples was performed by the following method. Siloxane-polyimide precursor solution: The rotational viscosity was measured at a temperature of 25 ± 0.1 ° C. using an E-type viscometer (VISCONIC EMD manufactured by Tokyo Keiki Co., Ltd.). Also,
The rotational viscosity after 7 days at room temperature was measured and the change over time was examined. Siloxane-polyimide cocondensate: Pencil hardness (JIS K5400) of the surface of the film was measured. The coating properties were determined by visually observing the film formed by the above baking, (1) that the film was formed with a substantially uniform thickness over the entire surface of the glass plate, (2) that the film surface was smooth, and (3) It was judged as “good” because no crack was generated. The silica content was measured using a thermobalance TG / Seiko Denshi Kogyo Co., Ltd.
The residual weight when the temperature was raised from room temperature to 1000 ° C. at a rate of 10 ° C./min using DTA220 was defined as “silica content”.

(Example 1) A 1-liter flask equipped with a stirrer, a thermometer, a condenser, and a nitrogen inlet tube was purged with nitrogen gas and then dehydrated and purified.
500 g of 2-pyrrolidone (hereinafter abbreviated as NMP),
129 g (0.949 mol) of methyltrimethoxysilane and 69.0 g (0.316 mol) of pyromellitic dianhydride (hereinafter abbreviated as PMDA) were mixed, and 6
The reaction was carried out at 0 ° C for 10 hours.
Dissolves into a clear solution. Next, 4-aminophenyltrimethoxysilane (hereinafter APM) was added to the reaction solution.
(Abbreviated as S) 135 g (0.633 mol) was added and the reaction was carried out for 5 hours to obtain a yellow and transparent siloxane-polyimide precursor solution of the present invention. The rotational viscosity of this solution is shown in Table 1.

Example 2 An N, N-dimethylacetamide (hereinafter referred to as DMA) was prepared using the same apparatus and method as in Example 1.
C), 149 g (0.836 mol) of methyltriethoxysilane and 60.8 of PMDA.
g (0.279 mol) were mixed and reacted at 50 ° C. for 20 hours. As a result, the powdery PMDA reacted and dissolved to form a transparent solution. Next, 123 g (0.557 mol) of 3-aminopropyltriethoxysilane (hereinafter abbreviated as APS-E) was added to the reaction solution, and the mixture was reacted for 7 hours. -A polyimide precursor solution was obtained. The rotational viscosity of this solution is shown in Table 1.

Example 3 Using the same apparatus and method as in Example 1, 500 g of NMP, 90.0 g (0.432 mol) of tetraethoxysilane, and 64.1 g (0.432 mol) of dimethyldiethoxysilane were used. ) And 3,3 ',
92.8 g (0.288 g) of 4,4′-benzophenonetetracarboxylic dianhydride (hereinafter abbreviated as BTDA)
Mol) and reacted at 65 ° C. for 8 hours.
A clear solution resulted. Next, 1 part of APMS was added to this reaction solution.
When 23 g (0.576 mol) was added and the reaction was carried out at 30 ° C. for 5 hours, a yellow and transparent siloxane-polyimide precursor solution of the present invention was obtained. The rotational viscosity of this solution is shown in Table 1.

Example 4 Using the same apparatus and method as in Example 1, 500 g of DMAC, 66.5 g (0.336 mol) of phenyltrimethoxysilane, and 36.0 g (0.112 mol) of BTDA were used. Mix and mix at 55 ° C for 10
When the reaction was performed for a time, a clear solution was obtained. next,
22.4 g (0.112 mol) of 4,4′-diaminodiphenyl ether (hereinafter abbreviated as DDE) was added to the reaction solution, and the mixture was reacted at 20 ° C. for 10 hours.
A clear yellow siloxane-polyimide precursor solution of the invention was obtained. The rotational viscosity of this solution is shown in Table 1.

Example 5 By the same apparatus and method as in Example 1, 500 g of DMAC, 148 g (0.744 mol) of phenyltrimethoxysilane and 7 g of BTDA were obtained.
When 9.9 g (0.248 mol) were mixed and reacted at 70 ° C. for 3 hours, a clear solution was obtained. Next, 106 g (0.496 mol) of APMS was added to this reaction solution, and the reaction was carried out at 50 ° C. for 6 hours. As a result, a yellow and transparent siloxane-polyimide precursor solution of the present invention was obtained.
The rotational viscosity of this solution is shown in Table 1.

(Example 6) By the same apparatus and method as in Example 1, 500 g of NMP, 36.4 g (0.184 mol) of phenyltrimethoxysilane and 2 g of PMDA were used.
After mixing 0.0 g (0.0917 mol) and performing a reaction at 60 ° C. for 7 hours, a transparent solution was obtained. Next, 16.1 g (0.0804 mol) of DDE and 4.89 g (0.0230 mol) of APMS were added to the reaction solution, and the mixture was reacted at 20 ° C. for 12 hours. A siloxane-polyimide precursor solution was obtained. The rotational viscosity of this solution is shown in Table 1.

Example 7 By the same apparatus and method as in Example 1, 500 g of DMAC, 217 g (1.09 mol) of phenyltrimethoxysilane and 5 g of BTDA were used.
When 0.3 g (0.156 mol) was mixed and reacted at 60 ° C. for 15 hours, a clear solution was obtained. Next, 66.5 g (0.312 mol) of APMS was added to this reaction solution, and the reaction was carried out at 30 ° C. for 10 hours. As a result, a yellow and transparent siloxane-polyimide precursor solution of the present invention was obtained. The rotational viscosity of this solution is shown in Table 1.

(Comparative Example 1) Using the same apparatus and method as in Example 1, 500 g of NMP and 42.2 g of DDE
(0.211 mol) and 46.0 g (0.2
11 mol), and the mixture was reacted at 30 ° C. for 8 hours. As a result, a transparent yellow polyamic acid solution was produced. The rotational viscosity of this solution is shown in Table 1.

Comparative Example 2 Using the same apparatus and method as in Example 1, 500 g of methyl carbitol, 55.56 g (0.267 mol) of tetraethoxysilane, and 6 parts of water
0.0 g and 5.5 g of acetic acid were mixed and reacted at 80 ° C. for 18 hours. At this time, no unreacted tetraethoxysilane was detected from the reaction solution, and a colorless and transparent tetraethoxysilane oligomer was produced.

Comparative Example 3 16.28 g of DDE in a mixed solvent of 300 g of NMP and 200 g of 2-methoxyethanol by the same apparatus and method as in Example 1.
(0.0813 mol) and 38.81 g (0.10 mol) of bis (3,4-dicarboxyphenyl) sulfone dianhydride
8 mol) and reacted at 20 ° C. for 5 hours.
11.41 of aminopropylmethyldiethoxysilane
g (0.0596 mol) was added and reacted at 90 ° C. for 2 hours. Further, 1.65 g (0.0108 mol) of tetramethoxysilane, 2.5 g of concentrated hydrochloric acid and 3 g of water were added to the solution, and the mixture was reacted at 50 ° C. for 10 hours.
At this point, no unreacted tetramethoxysilane was detected from the reaction solution, and a silicon-containing polyimide precursor solution was obtained.

[0040]

[Table 1] As is clear from the results in Table 1, the solution of the present invention composed of a non-aqueous solution has better viscosity stability than Comparative Examples 2 and 3 in which water was added to hydrolyze and condense alkoxysilane.

(Examples 8 to 14) Siloxane-polyimide cocondensate: Each of the siloxane-polyimide precursor solutions obtained in Examples 1 to 7 was applied as a coating solution on a slide glass plate by a spinner, and 100 After pre-drying at 250 ° C for 1 hour,
Baked for 1 hour at 400 ° C. for 1 to 2 μm comprising the siloxane-polyimide cocondensate of the present invention.
m was formed. The coating properties, pencil hardness, and silica content were measured, and the results are shown in Table 2.

(Comparative Examples 4 to 6) Using the silicon-containing polyimide precursor solutions obtained in Comparative Examples 1 to 3, sintering was carried out in the same manner as in Example 8 to form a film.
The silica content was measured and the results are shown in Table 2.

[0043]

[Table 2]

[0044]

The siloxane-polyimide precursor solution of the present invention is a good coating solution having excellent storage stability of viscosity, and the siloxane-polyimide co-condensate of the present invention obtained by firing this solution is As is easily deduced from the structure, an intermediate property between silica and polyimide is expected, and the coating film has improved silica film friability, and a coating film having higher hardness than the polyimide film can be obtained.

Claims (3)

(57) [Claims] 1. A reaction between a tetracarboxylic dianhydride represented by the following general formula (I) and an alkoxysilane represented by the following general formula (II) in an organic solvent. The diamine represented by (III) and the following general formula (I
V) The siloxane-polyimide precursor solution obtained by adding one or more of the aminosilanes represented by V) and reacting at a temperature of less than 150 ° C.
By heating to a temperature of 0 ° C., the solvent is volatilized, and an imidization reaction and a siloxane condensation reaction are performed. As a result, a cured siloxane-polyimide co-condensate is obtained. Embedded image Embedded image Embedded image Embedded image ｛However, in the general formulas (I), (II), (III) and (IV), R ¹ is independently tetravalent, R ² and R ³ are each independently
Valence, R ⁴ , R ⁵ , R ⁶ and R ⁷ represent a monovalent organic group,
m and n are 1 <m, n ≦ 4４. 2. A reaction between a tetracarboxylic dianhydride represented by the following general formula (I) and an alkoxysilane represented by the following general formula (II) in an organic solvent. A diamine represented by III) and the following general formula (IV)
Adding one or more of the aminosilanes represented by
A siloxane-polyimide precursor solution obtained by reacting at a temperature of less than 50 ° C. Embedded image Embedded image Embedded image Embedded image ｛Wherein, in the general formulas (I), (II), (III) and (IV), R ¹ is tetravalent, R ² and R ³ are divalent,
R ⁴ , R ⁵ , R ⁶ and R ⁷ represent a monovalent organic group, and m and n are 1 <m, n ≦ 4. 3. A reaction between a tetracarboxylic dianhydride represented by the following general formula (I) and an alkoxysilane represented by the following general formula (II) in an organic solvent. A diamine represented by III) and the following general formula (IV)
Adding one or more of the aminosilanes represented by
A method for producing a siloxane-polyimide precursor solution, which comprises reacting at a temperature of less than 50 ° C. Embedded image Embedded image Embedded image Embedded image ｛Wherein, in the general formulas (I), (II), (III) and (IV), R ¹ is tetravalent, R ² and R ³ are divalent,
R ⁴ , R ⁵ , R ⁶ and R ⁷ represent a monovalent organic group, and m and n are 1 <m, n ≦ 4.