JPH1170364A - Organic-inorganic composite film with high adhesion strength and method for forming film thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the adhesion strength of a coating to an electrode wiring formed on a coated film by producing a composite coating solution by mixing a resin solution containing a polyimide-type substance with a specified formula and polyimide precursor and a methaloxane polymer solution, applying the coating solution to the surface of a substrate, and thermally hardening the applied coating. SOLUTION: A resin solution is produced by dissolving polyimide precursors selected from polyimides and tetracarboxylic acids and their derivatives having the formula I and the formula II [wherein R1 , R3 , R5 , R7 respectively stand for tetravelent organic groups to compose tetracarboxylic acids or their derivatives; R2 , R6 , for divalent 6-22C organic groups having no long chain alkyl group; R4 , R8 for divalent 6-22C organic groups having long chain alkyl group; L/M = O/P = (100/0)-(70/30)]. The obtained resin solution is mixed with a methaloxane polymer solution containing a metal alkoxide having the formula III (wherein M is Si, Al or the like or Y; Z stands for the valence of the element; R9 is 1-5C alkyl) to give a composite coating solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a novel high-adhesion organic-inorganic composite film used in electric and electronic devices, particularly LCDs and semiconductors, and a method for producing the same. More specifically, it is used for an insulating film such as a junction coat, a passivation, a moisture proof, a buffer coat, an α-ray shielding, and an interlayer insulation, and is an organic film having excellent adhesion to an electrode formed thereon. An inorganic composite membrane is provided.

[0002]

2. Description of the Related Art Conventionally, polyimide has excellent heat resistance and electrical insulation properties.
It is used for a liquid crystal alignment film for D, an insulating film for semiconductor, and the like. On the other hand, metalloxane polymers are used as raw materials for glass, ceramics, fibers, inorganic paints and the like, or as special coating agents.

Conventionally, various inorganic raw materials such as silica and silicone resins have been blended for the purpose of improving the strength and elastic modulus of a polyimide resin. In the composite film obtained by such a method, although a film in which inorganic components are uniformly dispersed is obtained, sufficient adhesion to wirings such as electrodes formed on the top cannot be obtained, and peeling or cracking of electrodes occurs. Resulting in.

JP-A-6-65375 discloses that a silane compound having an amino group is added to a polyimide resin,
A heat-resistant composite material having a hydrolytic reaction in the presence of water to synthesize a composite material, further improving the original good electrical properties and mechanical properties of polyimide, and imparting heat resistance, adhesion and surface properties has been disclosed. I have. JP-A-58-197847 discloses that in forming a multilayer wiring structure on a semiconductor substrate, a polyimide film is formed on a substrate, heated at a temperature of 100 to 400 ° C., and a titanium chelate compound is further formed on the polyimide film. Is applied and heated at a temperature of 350 ° C. to form a composite film of a polyimide film and a titanium oxide film, suppressing migration of impurity ions in the polyimide film, preventing moisture absorption of the polyimide film, and adhering to the upper metal film. A composite membrane having improved properties is disclosed.

[0005] Japanese Patent Application Laid-Open No. 1-138787 discloses that aromatic polyimide has an inorganic fine powder having an average particle diameter of 1 μm or less.
It discloses that a wiring board having excellent adhesion and flexibility can be obtained without using an adhesive layer between a metal thin film and a metal thin film.

[0006]

SUMMARY OF THE INVENTION The above-mentioned Japanese Patent Application Laid-Open No. 6-653.
In the method described in No. 75, although a siloxane compound is generated by the hydrolysis reaction of the silane compound, the amino group of the silane compound reacts with the polyimide to form a siloxane bond-containing polyimide. The siloxane compound is uniformly present in the film, and sufficient adhesion to the upper metal electrode cannot be obtained unless a large amount of the siloxane compound is added. However, when the polyimide and the silane compound are reacted, the molecular weight is increased to increase the viscosity of the solution or the solubility in the solvent is reduced, so that a problem that only a small amount of the silane compound is mixed occurs.

In the method described in Japanese Patent Application Laid-Open No. 197847/1983, a titanium oxide film is formed on a polyimide film. Therefore, although a titanium oxide film has high adhesion to an upper electrode formed thereon, polyimide is applied. After calcination, further application and calcination of the titanium oxide film are repeated in the same manner, so that not only the number of steps becomes inefficient, but also that the solvent of the titanium chelate compound does not dissolve the polyimide film must be selected. Is created.

In the method described in Japanese Patent Application Laid-Open No. 1-138787, since the inorganic fine powder is mixed with the polyimide, the compatibility is poor, phase separation occurs, and the transparency is reduced. In addition, the dispersibility of the inorganic fine powder is poor, partial aggregation occurs, and the surface of the coating film becomes uneven, and the adhesion to the upper electrode varies. An object of the present invention is to solve the above problems, simply and efficiently, mix a polyimide and / or a polyimide precursor and a metalloxane polymer, form a coating film on a substrate, and form an inorganic coating on the coating film surface. An object of the present invention is to provide an organic-inorganic composite film having high adhesion to an electrode wiring formed on a coating film by segregating a metalloxane polymer as a component and a method for forming the same.

[0009]

Means for Solving the Problems The following general formula (1)

[0010]

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(Wherein R ₁ and R ₃ are tetravalent organic groups constituting tetracarboxylic acid and derivatives thereof, and R ₂ is a divalent organic group having no long-chain alkyl group having 6 to 22 carbon atoms.) R ₄ is a divalent organic group having a long-chain alkyl group having 6 to 22 carbon atoms, L / M = 100/0 to 70 /
30) a polyimide having a repeating unit represented by formula (30) and / or the following general formula (2)

[0012]

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(Wherein R ₅ and R ₇ are tetravalent organic groups constituting tetracarboxylic acid and derivatives thereof, and R ₆ is a divalent organic group having no long-chain alkyl group having 6 to 22 carbon atoms.) R ₈ is a divalent organic group having a long-chain alkyl group having 6 to 22 carbon atoms, and O / P = 100/0 to 70 /.
30) the polyimide and / or the polyimide precursor resin solution obtained by dissolving a polyimide precursor having one or more kinds of repeating units selected from tetracarboxylic acids and derivatives thereof in an organic solvent; The following general formula (3)

[0014]

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(Where M is Si, Al, Ti, Zr, I
It is an element of n, Sn, Sb, Ba, Nb or Y, and Z is a valence of the element. R ₉ is an alkyl group having 1 to 5 carbon atoms. ), A metalloxane polymer solution obtained by polymerizing one or more metal alkoxides in an organic solvent with a metalloxane polymer solution based on 100 parts by weight of the solid content of the polyimide and / or polyimide precursor resin solution. The xanthic polymer was mixed so as to be 0.5 to 100 parts by weight in terms of solid content in terms of oxide to form an organic-inorganic composite coating solution, and then the solution was applied to the surface of a substrate, thereby obtaining By heat curing the coating at 80-450 ° C. As a result, a highly adhesive organic-inorganic composite film characterized by segregating the metalloxane polymer component on the coating film surface is formed. The composite film shows high adhesion to the electrode wiring formed on the composite film.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In general, a polyimide and / or a polyimide precursor are generally prepared by reacting and polymerizing a tetracarboxylic acid derivative with a primary diamine to obtain a polyimide precursor, and ring-closing imidization to obtain a polyimide. is there. In the present invention, as a raw material for polymerizing polyimide and / or a polyimide precursor, a diamine component has 6 to 6 carbon atoms in a side chain.
By using a specific ratio of a diamine having no long-chain alkyl group of 22 and a diamine having a long-chain alkyl group of 6 to 22 carbon atoms in a side chain, a metalloxane polymer is applied to the surface of the coating film intended for the present invention. A highly adhesive organic-inorganic composite film in which components are segregated can be obtained.

Specific examples of tetracarboxylic acid derivatives as a raw material for polymerizing polyimide and / or a polyimide precursor include pyromellitic acid, 2,3,6,7-
Naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,5 6-anthracenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid,
Bis (3,4-dicarboxyphenyl) ether, 3,
3 ', 4,4'-benzophenonetetracarboxylic acid, bis
(3,4-dicarboxyphenyl) sulfone, bis
(3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,
1,1,3,3,3-hexafluoro-2,2-bis
(3,4-dicarboxyphenyl) propane, bis
(3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,
Aromatic tetracarboxylic acids such as 6-bis (3,4-dicarboxyphenyl) pyridine and their dianhydrides and their dicarboxylic diacid halides;
3,4-cyclobutanetetracarboxylic acid, 1,2,3
4-cyclopentanetetracarboxylic acid, 1,2,4,5
Alicyclic tetracarboxylic acids such as -cyclohexanetetracarboxylic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid and the like; Dianhydrides and their dicarboxylic diacid halides,
Examples thereof include aliphatic tetracarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid, dianhydrides thereof, dicarboxylic acid diacid halides thereof, and the like.

The effect of the present invention is to use a diamine having a long-chain alkyl group having 6 to 22 carbon atoms in the side chain as a diamine component as a raw material for polymerizing polyimide and / or a polyimide precursor. Is important in getting By adjusting the amount of the diamine having a long-chain alkyl group having 6 to 22 carbon atoms in the side chain to be 30 mol% or less of the total diamine, it is possible to obtain a coating film in which the inorganic component is segregated on the film surface. .

Specific examples of the diamine having a long-chain alkyl group having 6 to 22 carbon atoms in the side chain include 4,4'-diamino-3-dodecyldiphenyl ether, 1-dodecanoxy-2,4-diaminobenzene, Octadecanoxy
2,4-diaminobenzene, 1,1-bis (4-aminophenyl) cyclohexane, 2,2-bis [4- (4-
Examples thereof include diamines having a long-chain alkyl group having 6 to 22 carbon atoms such as aminophenoxy) phenyl] octane or a cycloalkyl group. One or more of these diamines may be used in combination.

Specific examples of the diamine having no long-chain alkyl group having 6 to 22 carbon atoms in the side chain include p-phenylenediamine, 1,4-bis (4-aminophenyl) benzene, 4,4 ′ -Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-
Dihydroxy-4,4'-diaminobiphenyl, 3,
3'-dichloro-4,4'-diaminobiphenyl, 3,
3′-dicarboxy-4,4′-diaminobiphenyl,
4,4′-bis (4-aminophenoxy) biphenyl,
Diaminodiphenylmethane, diaminodiphenylether, 2,2-diaminodiphenylpropane, 4,4′-
Diaminodiphenyl sulfone, diaminobenzophenone, 1,3-bis (4-aminophenoxy) benzene,
1,4-bis (4-aminophenoxy) benzene, 4,
4'-di (4-aminophenoxy) diphenylsulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2- Aromatic diamines such as bis [4- (4-aminophenoxy) phenyl] propane; alicyclic diamines such as diaminodicyclohexylmethane, diaminodicyclohexyl ether and diaminocyclohexane; and 1,2-diaminoethane and 1,3-diaminopropane And aliphatic diamines such as 1,4-diaminobutane and 1,6-diaminohexane. One or more of these diamines may be used in combination.

The diamine component is represented by the following general formula (4)

[0022]

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(Wherein R ₁₀ is a divalent organic group), diamines having an amino group at the para-position of a benzene ring, diaminobenzene derivatives and diaminobiphenyl derivatives are particularly preferred. The use of this diamine improves the thermal stability of the coating film, and in practice, can improve the adhesiveness when the upper electrode is formed and its thermal stability. Specific examples of particularly preferred diamines having a long-chain alkyl group having 6 to 22 carbon atoms in this side chain include:
4,4′-diamino-3-dodecyldiphenyl ether, 1,1-bis (4-aminophenyl) cyclohexane, and 2,2-bis [4- (4-aminophenoxy) phenyl] octane. Further, the side chain has 6 to 6 carbon atoms.
Specific examples of particularly preferred diamines having no long-chain alkyl group of 22 include p-phenylenediamine, 1,4
-Bis (4-aminophenyl) benzene, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-
Diaminobiphenyl, 3,3′-dihydroxy-4,
4'-diaminobiphenyl, 3,3'-dichloro-4,
4'-diaminobiphenyl, 3,3'-dicarboxy-
4,4'-diaminobiphenyl, 4,4'-bis (4-
Aminophenoxy) biphenyl, diaminodiphenylmethane, diaminodiphenylether, 2,2-diaminodiphenylpropane, 4,4′-diaminodiphenylsulfone, diaminobenzophenone, 1,3-bis (4-
Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-di (4-aminophenoxy) diphenylsulfone, 2,2-bis [4-
(4-aminophenoxy) phenyl] propane, 1,
Aromatic diamines such as 1,1,3,3,3-hexafluoro-2,2-bis [4- (4-aminophenoxy) phenyl] propane are exemplified.

A polyimide precursor is prepared by reacting and polymerizing a tetracarboxylic acid derivative with a diamine. In this case, a tetracarboxylic dianhydride is generally used as the tetracarboxylic acid derivative used. The molar ratio of tetracarboxylic dianhydride to diamine is preferably 0.8 to 1.2. As in the ordinary polycondensation reaction, the molar ratio is 1
The degree of polymerization of the produced polymer increases as the value is closer to.

If the degree of polymerization is too low, the strength of the polyimide coating film is insufficient, and if the degree of polymerization is too high, the workability during the formation of the polyimide coating film may deteriorate. The above-mentioned polyimide and / or polyimide precursor consist of a resin solution dissolved in an organic solvent, and the solvent is polyimide and / or
Alternatively, there is no particular limitation as long as it dissolves the polyimide precursor.

Examples thereof include 2-pyrrolidone, N-methylpyrrolidone, N, N-dimethylacetamide, N, N
-Dimethylformamide, dimethylsulfoxide, hexamethylphosphoramide, γ-butyrolactone and the like. In addition, a solvent which does not dissolve the polyimide and / or the polyimide precursor by itself may be added to the above solvent as long as the solubility is not impaired.

The method of dissolving these polyimides and / or polyimide precursors in the above solvent to form a resin solution is not particularly limited. For example, the above-mentioned reaction and polymerization solution of the polyimide and / or the polyimide precursor may be used as it is, or the resulting polyimide and / or the polyimide precursor may be poured into a large excess of water or a solvent such as methanol,
After recovering the precipitate, it may be used after being dissolved again in the above-mentioned solvent.

The solid content of the polyimide and / or polyimide precursor resin solution used in the present invention is calculated from the residual weight after drying at 200 ° C., and the solid content of the polyimide and / or polyimide precursor resin solution is uniform. There is no particular limitation as long as a solution is formed. The metal element M contained in the general formula (3) is not particularly limited.
i, Al, Ti, Zr, In, Sn, Sb, Ba, N
b, Y, etc., and examples of the alkyl group R include methyl, ethyl, propyl, butyl, and pentyl. Examples of preferable metal alkoxides include tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane. Alkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, butyltrimethoxysilane, trifluoropropyltrimethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane; aluminum such as aluminum tripropoxide and aluminum triisopropoxide Alkoxides, titanium tetraethoxide, titanium tetraisopropoxide, titanium alkoxides such as titanium tetrabutoxide, zirconium tetraethoxide, zirconium Torapuropokishido, zirconium alkoxides such as zirconium tetrabutoxide, indium trimethoxide, indium triethoxide,
Indium alkoxides such as indium tripropoxide; tin alkoxides such as tin tetraethoxide and tin tetramethoxide; antimony alkoxides such as antimony triethoxide and antimony tripropoxide; barium diethoxide and barium dipropoxide Barium alkoxides, niobium pentamethoxide, niobium pentaethoxide, niobium alkoxides such as niobium pentabutoxide, yttrium trimethoxide, yttrium alkoxides such as yttrium tripropoxide, etc. Can be Further, chelate compounds in which β-diketones such as acetylacetone and benzoylacetone are coordinated with these metal alkoxides may be used. Among these, tetramethoxysilane, tetraethoxysilane, aluminum triisopropoxide, titanium tetraisopropoxide, and zirconium tetrabutoxide are particularly preferable.

The metalloxane polymer solution of the present invention is obtained by polymerizing a metal alkoxide represented by the general formula (3) in an organic solvent, and the solution contains a transparent, gel-like metalloxane polymer. I haven't. The polymerization reaction is not particularly limited as long as it is a reaction method for forming a metalloxane polymer from the metal alkoxide represented by the general formula (3).

The reaction method for forming the metalloxane polymer is preferably an ordinary hydrolysis reaction using a metal alkoxide represented by the general formula (3), an organic solvent, a catalyst and water. The catalyst for performing the hydrolysis reaction is hydrochloric acid, nitric acid,
An acid catalyst such as oxalic acid is used. The amount of the acid catalyst used for forming the metalloxane polymer solution is preferably 0.5 to 30 mol%, more preferably 1 to 10 mol%, based on 1 mol of the metal alkoxide. The amount of water used to form the metalloxane polymer solution is preferably 1 to 10 mol, and particularly preferably 2 to 5 mol, per 1 mol of the metal alkoxide. When the amount of the hydrolysis water is less than 1 mol, the reaction does not proceed sufficiently and the metalloxane polymer is not formed. If more than 10 moles of hydrolyzed water is used, precipitation of a polymer occurs when mixing with a polyimide and / or a polyimide precursor resin solution, or the stability of the organic-inorganic composite coating solution is reduced.

The metalloxane polymer can be formed by a non-aqueous reaction without using a catalyst or water. Examples include metalloxane polymer solutions with metal alkoxides, alcohol anhydrides and oxalic acid. The solid content of the metalloxane polymer in the present invention is calculated by calcining the metalloxane polymer solution at 550 ° C. to form an oxide with respect to the weight of the metalloxane polymer solution, and converting from the weight. The solid concentration of the metalloxane polymer is preferably from 1 to 20% by weight, particularly preferably from 4 to 12% by weight. If the amount is less than 1% by weight based on the oxide formed by the metalloxane polymer, the formation of the metalloxane polymer is poor, and unreacted monomers remain. 20 calculated from the oxide formed by the metalloxane polymer
If the content is more than 10% by weight, gelation tends to occur, which is not preferable.

The organic solvent used for forming the metalloxane polymer solution in the present invention is methanol, ethanol, propanol, butanol, ethylene glycol,
Propylene glycol, hexylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Propylene glycol monomethyl ether, propylene glycol monoethyl ether, γ-butyrolactone,
N-methylpyrrolidone and the like can be mentioned, and one kind or a combination of two or more kinds is used. The amount of solvent varies slightly depending on the type of metalloxane polymer or organic solvent to be formed,
The solvent is preferably 1 to 100 mol, and particularly preferably 5 to 50 mol, per 1 mol of the metal alkoxide. If the solvent is used in an amount less than 1 mol per 1 mol of the metal alkoxide, the concentration of the metalloxane polymer becomes high and gelation easily occurs. If the solvent is used in an amount of more than 100 moles relative to 1 mole of the metal alkoxide, the resulting metalloxane polymer solution has an insufficient concentration in terms of oxide, and requires concentration before coating, which is not efficient.

When mixing with the polyimide and / or the polyimide precursor resin solution, if the solvent of the metalloxane polymer solution is a solvent that causes gelling or precipitation of the polyimide and / or the polyimide precursor resin, it is preliminarily noted. The solvent of the metalloxane polymer solution may be replaced with another solvent and mixed with the polyimide and / or polyimide precursor resin solution. Further, after forming the metalloxane polymer, the metalloxane polymer may be concentrated for the purpose of changing the concentration or diluted with a solvent.

The mixing of the polyimide and / or the polyimide precursor resin solution and the metalloxane polymer solution is not particularly limited, but may be agitated for about 5 to 30 minutes for uniform mixing. The mixing ratio is such that the metalloxane polymer is 0.5 to 10 in terms of oxide based on 100 parts by weight of the solid content of the polyimide and / or the polyimide precursor resin solution.
The amount is preferably 0 parts by weight, and particularly preferably 3 to 40 parts by weight. If the metalloxane polymer is less than 0.5 parts by weight in terms of oxide, when the coating is formed, sufficient adhesion to the upper electrode wiring is obtained because the metalloxane polymer component as an inorganic component segregating on the surface is small. Absent. On the other hand, if the amount of the metalloxane polymer is more than 100 parts by weight in terms of oxide, the coating film is phase-separated and the transparency is undesirably reduced.

An organic-inorganic composite coating solution is applied to the surface of a substrate, and the resulting coating film is thermally cured at 80 to 450 ° C. to segregate the metalloxane polymer component on the coating film surface. Increasing the amount of water and alcohol in the medium of the composite coating solution increases the effect of promoting segregation. As for the segregation effect of the solvent, the stronger the hydrophilicity, the greater the effect of segregation. Therefore, the distribution of the metalloxane polymer component segregated on the coating film surface can be controlled by selecting water and alcohol and adjusting the addition amount.

The substrate used in the present invention is not particularly limited as long as it allows the formation of an adhesive film thereon. Particularly, in order to form an organic-inorganic composite film, glass or glass with a transparent electrode is used. Substrates such as plastic, silicon wafers and the like are desirable. Organic-inorganic composite coating solution
It can be applied to a substrate by a usual method, for example, a dip method, a spin coating method, a brush coating method, a roll coating method, a flexographic printing method, or the like.

The coating film formed on the substrate may be heat-cured as it is. However, prior to this, the coating film is dried at room temperature to 80 ° C., preferably at 50 to 80 ° C., and then dried at 80 to 450 ° C., preferably Heated at 100-350 ° C. About 5 to 60 minutes is sufficient as the heating time. When the heating temperature is lower than 80 ° C., the hardness of the obtained coating film is insufficient. Generally, it is preferable to heat a substrate having heat resistance such as glass or a silicon wafer at a temperature of 300 ° C. or more. At a temperature higher than 450 ° C., the organic-inorganic composite film is thermally decomposed, and no film is formed. These heatings can be performed by a usual method, for example, a hot plate, an oven, a belt furnace, or the like.

The electrode formed on the organic-inorganic composite film in the present invention is not particularly limited as long as it has conductivity, and examples thereof include aluminum, gold, silver, copper, platinum, and platinum.
Metals such as nickel, iron, molybdenum, indium and I
Oxides, such as TO and ATO, are mentioned. The organic-inorganic composite film obtained by the present invention needs to mix a polyimide and / or a polyimide precursor resin with a metalloxane polymer. When the polyimide and / or the polyimide precursor resin and the monomer metal alkoxide represented by the general formula (3) are directly mixed, for example, tetramethoxysilane or tetraethoxysilane has a high volatility, and a coating film of 8% is used.
After thermosetting at 0-450 ° C., it is not present in the film. Therefore, it is necessary to hydrolyze the metalloxane polymer in advance.

The organic-inorganic composite film obtained according to the present invention comprises:
By not allowing the polyimide and / or the polyimide precursor resin to react with the metalloxane polymer, it becomes possible to segregate the metalloxane polymer on the surface of the coating film when forming the coating film. Thereby, high adhesion with the electrode formed on the upper part is developed. Conversely, if the metalloxane polymer has a reactive group such as an epoxy group, an acrylic group, or an amino group, it reacts with the polyimide and / or the polyimide precursor resin, and when formed into a coating film, the metalloxane polymer segregates on the surface. It exists uniformly in the film without. As a result, a composite film having insufficient adhesion to the upper electrode is obtained.

[0040]

The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to the following Examples. Example 1 12.6 g of 1,3-bis (4-aminophenoxy) benzene and 70 g of N-methylpyrrolidone were added to a 200 mL four-necked flask, and mixed well with stirring at room temperature. Next, a solution prepared by dissolving 8.1 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride in 47 g of N-methylpyrrolidone was added thereto, and the mixture was stirred and reacted at room temperature for 4 hours to give a solid content of 15% by weight. Was prepared.

Next, 11.3 g of tetraethoxysilane, 17.2 g of ethanol, 0.24 g of oxalic acid, and 3.9 g of water were sequentially added to a 100-mL eggplant flask, and the mixture was stirred at room temperature for 30 minutes to react, and a metalloxane polymer solution ( (Solid content: 10% by weight). 50 g of the above polyimide precursor resin solution was added to another 100 mL eggplant-shaped flask, 25 g of the above metalloxane polymer solution was added, and stirred and mixed for 30 minutes to form an organic-inorganic composite coating solution. A few drops of this coating solution are dropped on a silicon wafer, and 4000 rpm
m for 20 seconds, dried on a hot plate at 80 ° C. for 5 minutes, and dried in an oven at 300 ° C. for 30 minutes.
By performing partial firing, an organic-inorganic composite film was formed.

The thickness of the organic-inorganic composite film was measured by a film thickness measuring device (Taristep, manufactured by Rank Taylor Hobson). The film thickness was 2 μm. In X-ray photoelectron spectroscopy (argon ion sputtering measurement mode) using an X-ray photoelectron spectrometer (manufactured by Shimadzu Corporation: ESCA-3200), S was applied from the surface of the composite film toward the inside.
The element distributions of i (2s) and N (1s) were measured. It was confirmed that the silica component was an organic-inorganic composite film segregated on the surface.

Further, on this organic-inorganic composite film, a vacuum evaporation apparatus (JEOL Co., Ltd., high vacuum evaporation apparatus JEE-4X)
And a few drops of a resist (S1400-21, manufactured by Shipley Co., Ltd.)
It was spin-coated at 0 rpm for 20 seconds, dried on a hot plate at 90 ° C. for 90 seconds, and exposed and developed through a pattern mask to pattern the resist. Then, the aluminum electrode was immersed in a solution of phosphoric acid: nitric acid = 2: 1 for 5 minutes to etch the aluminum, the resist was stripped, and an aluminum electrode pattern was formed on the organic-inorganic composite film.

When this substrate was observed with an optical microscope,
No peeling or cracking of the aluminum electrode was observed, indicating good adhesion between the organic-inorganic composite film and the aluminum electrode. Example 2 In a 100 mL eggplant-shaped flask, 9.3 g of methyltriethoxysilane, 17.9 g of propylene glycol, and 0.1 g of oxalic acid were added.
24 g and 3.9 g of water were sequentially added, and the mixture was stirred and reacted at room temperature for 30 minutes to prepare a metalloxane polymer solution (solid content concentration: 10% by weight).

In the same manner as in Example 1, a polyimide precursor resin solution and a metalloxane polymer solution were mixed, applied, dried and fired to form an organic-inorganic composite film. Further, the same organic-inorganic composite film as in Example 1 was evaluated. The film thickness of this organic-inorganic composite film was 2.2 μm, and it was confirmed by X-ray photoelectron spectroscopy analysis that the silica component was an organic-inorganic composite film having segregated on the surface.

Further, aluminum deposition, resist patterning, aluminum etching, and resist stripping were performed in the same manner as in Example 1 to form an aluminum electrode pattern on the organic-inorganic composite film. When the substrate was observed with an optical microscope, no peeling or cracking of the aluminum electrode was observed, indicating good adhesion between the organic-inorganic composite film and the aluminum electrode.

Example 3 5.7 Tetraethoxysilane was placed in a 100 mL eggplant-shaped flask.
g, 4.8 g of methyltriethoxysilane, 18.0 g of N-methylpyrrolidone, 0.24 g of oxalic acid, and 3.9 g of water were sequentially added, and the mixture was stirred and reacted at room temperature for 30 minutes to give a metalloxane polymer solution (solid content concentration). 10% by weight).

In the same manner as in Example 1, a polyimide precursor resin solution and a metalloxane polymer solution were mixed, applied, dried and fired to form an organic-inorganic composite film. Further, the same organic-inorganic composite film as in Example 1 was evaluated. The film thickness of this organic-inorganic composite film was 2.3 μm, and it was confirmed by X-ray photoelectron spectroscopy analysis that the silica component was an organic-inorganic composite film segregated on the surface.

Further, in the same manner as in Example 1, aluminum was deposited, a resist was patterned, aluminum was etched, and the resist was peeled off to form an aluminum electrode pattern on the organic-inorganic composite film. When the substrate was observed with an optical microscope, no peeling or cracking of the aluminum electrode was observed, indicating good adhesion between the organic-inorganic composite film and the aluminum electrode.

Example 4 In a 200 mL four-necked flask, 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane 17.7 g and N
-Methylpyrrolidone (100 g) was added and mixed well at room temperature. Next, 8.3 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride was added to N-methylpyrrolidone 4
A solution dissolved in 7 g was added, and the mixture was stirred and reacted at room temperature for 4 hours to prepare a polyimide precursor resin solution having a solid content of 15% by weight.

In the same manner as in Example 1, a polyimide precursor resin solution and a metalloxane polymer solution were mixed, applied, dried and fired to form an organic-inorganic composite film. Further, the same organic-inorganic composite film as in Example 1 was evaluated. The film thickness of this organic-inorganic composite film was 2.0 μm, and it was confirmed by X-ray photoelectron spectroscopy analysis that the silica component was an organic-inorganic composite film segregated on the surface.

Further, in the same manner as in Example 1, deposition of aluminum, patterning of resist, etching of aluminum, and peeling of the resist were performed to form an aluminum electrode pattern on the organic-inorganic composite film. When the substrate was observed with an optical microscope, no peeling or cracking of the aluminum electrode was observed, indicating good adhesion between the organic-inorganic composite film and the aluminum electrode.

Example 5 In a 200 mL four-necked flask, 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane 14.2 g, 1
-Octadecanoshiki-2,4-diaminobenzene 3.2
5 g and N-methylpyrrolidone were added and mixed well with stirring at room temperature. Next, a solution prepared by dissolving 8.3 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride in 47 g of N-methylpyrrolidone was added thereto, and the mixture was stirred at room temperature for 4 hours to be reacted to obtain a solid content of 15% by weight. Was prepared.

In the same manner as in Example 1, a polyimide precursor resin solution and a metalloxane polymer solution were mixed, applied, dried and fired to form an organic-inorganic composite film. Further, the same organic-inorganic composite film as in Example 1 was evaluated. The film thickness of this organic-inorganic composite film was 2.1 μm, and it was confirmed by X-ray photoelectron spectroscopic analysis that the silica component was an organic-inorganic composite film segregated on the surface.

Further, aluminum deposition, resist patterning, aluminum etching and resist peeling were performed in the same manner as in Example 1 to form an aluminum electrode pattern on the organic-inorganic composite film. When the substrate was observed with an optical microscope, no peeling or cracking of the aluminum electrode was observed, indicating good adhesion between the organic-inorganic composite film and the aluminum electrode.

Comparative Example 1 In a 200 mL four-necked flask, 12.6 g of 1,3-bis (4-aminophenoxy) benzene and bis (γ-aminopropyl) -1,1,3,3-tetramethyldisiloxane were added. 56 g and N-methylpyrrolidone 70 g were added and mixed well at room temperature. Next, a solution prepared by dissolving 8.1 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride in 47 g of N-methylpyrrolidone was added thereto, and the mixture was stirred and reacted at room temperature for 4 hours to give a solid content of 15% by weight. Was prepared.

The above-mentioned polyimide precursor resin solution was coated, dried and fired in the same manner as in Example 1 without adding the metalloxane polymer solution to form a polyimide film.
Further, the same organic-inorganic composite film as in Example 1 was evaluated.
The thickness of this polyimide film was 3 μm, and bis (γ-aminopropyl) -1,1,3,3 was determined by X-ray photoelectron spectroscopy.
-It was confirmed that the siloxane component derived from tetramethyldisiloxane did not segregate on the surface and was uniformly dispersed in the film. This indicates that the polyimide resin has reacted with the silane compound.

Further, in the same manner as in Example 1, aluminum was deposited, the resist was patterned, the aluminum was etched, and the resist was peeled off to form an aluminum electrode pattern on the polyimide film. When the substrate was observed with an optical microscope, peeling and cracking of the aluminum electrode were observed, and the adhesion between the polyimide film and the aluminum electrode was insufficient.

Comparative Example 2 In a 200 mL four-necked flask, 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane 7.06 g, 1
Octadecanoshiki-2,4-diaminobenzene 9.7
1 g and N-methylpyrrolidone were added and mixed well with stirring at room temperature. Next, a solution prepared by dissolving 8.3 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride in 47 g of N-methylpyrrolidone was added thereto, and the mixture was stirred at room temperature for 4 hours to be reacted to obtain a solid content of 15% by weight. Was prepared.

In the same manner as in Example 1, a polyimide precursor resin solution and a metalloxane polymer solution were mixed, applied, dried and fired to form an organic-inorganic composite film. Further, the same organic-inorganic composite film as in Example 1 was evaluated. The film thickness of this organic-inorganic composite film was 2.2 μm, and it was confirmed by X-ray photoelectron spectroscopy analysis that the silica component was an organic-inorganic composite film having segregated on the surface.

Further, in the same manner as in Example 1, aluminum was deposited, a resist was patterned, aluminum was etched, and the resist was peeled off, thereby forming an aluminum electrode pattern on the organic-inorganic composite film. When the substrate was observed with an optical microscope, peeling of the aluminum electrode was partially observed.

[0062]

According to the present invention, by combining a metalloxane polymer with a polyimide, an organic-inorganic composite film in which inorganic components are easily segregated on the surface can be easily obtained by a single application and baking when forming a film. Since the inorganic component exists in the surface layer of the coating, the adhesion to the electrode wiring formed on the coating is improved. Further, in the present invention, it can be used as a high-adhesion interlayer insulating film or a high-adhesion flattening film in the LCD and semiconductor fields by being applied to a glass substrate or a silicon wafer.

[Brief description of the drawings]

FIG. 1 is an X-ray photoelectron spectroscopy (argon ion sputtering measurement mode) spectrum diagram of an organic-inorganic composite film formed in Example 1.

[Explanation of symbols]

 1: Spectrum of Si (2s) element 2: Spectrum of N (1s) element

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09D 185/00 C09D 185/00 // (C09D 179/08 183: 02 185: 00) (72) Inventor Takakazu Nakata Funabashi, Chiba Prefecture 722-1, Tsuboi-cho, Nissan Chemical Research Institute, Central Research Laboratory (72) Inventor Kenichi Motoyama 722-1, Tsuboi-cho, Funabashi-shi, Chiba Prefecture, Central Research Laboratory of Nissan Chemical Industry Co., Ltd.

Claims (2)

[Claims] (1) The following general formula (1): (Wherein, R ₁ and R ₃ are tetravalent organic groups constituting tetracarboxylic acid and its derivatives, and R ₂ has 6 to ₂ carbon atoms.
2 is a divalent organic group having no long-chain alkyl group;
₄ is a divalent organic group having a long-chain alkyl group having 6 to 22 carbon atoms. L / M = 100/0 to 70/30) and / or a polyimide having a repeating unit represented by the following general formula (2): (Wherein, R ₅ and R ₇ are tetravalent organic groups constituting tetracarboxylic acid and its derivatives, and R ₆ has ₆ to 2 carbon atoms.
2 is a divalent organic group having no long-chain alkyl group;
₈ is a divalent organic group having a long-chain alkyl group having 6 to 22 carbon atoms. O / P = 100/0 to 70/30), a polyimide obtained by dissolving a polyimide precursor having one or more kinds of repeating units selected from tetracarboxylic acids and derivatives thereof in an organic solvent, and And / or the polyimide precursor resin solution and the following general formula (3): (Where M is Si, Al, Ti, Zr, In, Sn, S
b, Ba, Nb or Y element, and Z is the valence of the element. R ₉ is an alkyl group having 1 to 5 carbon atoms. ), A metalloxane polymer solution obtained by polymerizing one or more metal alkoxides in an organic solvent with a metalloxane polymer solution based on 100 parts by weight of the solid content of the polyimide and / or polyimide precursor resin solution. The solid content of the xanthate polymer is 0.5 to 100 in terms of oxide.
It is obtained by forming an organic-inorganic composite coating solution by mixing so as to be parts by weight, then applying the solution to a substrate surface, and thermally curing the resulting coating film at 80 to 450 ° C. A highly adherent organic-inorganic composite film, wherein a metalloxane polymer component is segregated on the surface of the coating film. 2. A compound represented by the following general formula (1): (Wherein, R ₁ and R ₃ are tetravalent organic groups constituting tetracarboxylic acid and its derivatives, and R ₂ has 6 to ₂ carbon atoms.
2 is a divalent organic group having no long-chain alkyl group;
₄ is a divalent organic group having a long-chain alkyl group having 6 to 22 carbon atoms. L / M = 100/0 to 70/30) and / or a polyimide having a repeating unit represented by the following general formula (2): (Wherein, R ₅ and R ₇ are tetravalent organic groups constituting tetracarboxylic acid and its derivatives, and R ₆ has ₆ to 2 carbon atoms.
2 is a divalent organic group having no long-chain alkyl group;
₈ is a divalent organic group having a long-chain alkyl group having 6 to 22 carbon atoms. O / P = 100/0 to 70/30), a polyimide obtained by dissolving a polyimide precursor having one or more kinds of repeating units selected from tetracarboxylic acids and derivatives thereof in an organic solvent, and And / or the polyimide precursor resin solution and the following general formula (3): (Where M is Si, Al, Ti, Zr, In, Sn, S
b, Ba, Nb or Y element, and Z is the valence of the element. R is an alkyl group having 1 to 5 carbon atoms. A) a metalloxane polymer solution obtained by polymerizing one or more metal alkoxides represented by the formula (1) in an organic solvent; and 100 parts by weight of the solid content of the polyimide and / or polyimide precursor resin solution. The organic polymer composite solution is mixed by mixing the xan polymer in an amount of 0.5 to 100 parts by weight in terms of solid content in terms of oxide to form an organic-inorganic composite coating solution. A method for forming a highly adhesive organic-inorganic composite film, wherein a metalloxane polymer component is segregated on the surface of a coating film, wherein the film is thermally cured at 80 to 450 ° C.