JPH11217502A - Photosensitive polyimide precursor solution, polyimide coated film obtained therefrom and production of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject solution readily producible, not containing any inorganic salt nor inorganic ion and having a high concentration and a low viscosity by dissolving a salt of a specific compound having amino groups and a specific compound and a sensitizer, or the like, as solutes in a solvent. SOLUTION: This solution is obtained by dissolving a salt between a compound having amino groups of the formula: H2 N-R-R-NH2 (R is a bifunctional aromatic residue having at least one 6-membered carbon ring) and a compound of the formula [R' is a tetrafunctional aromatic residue having at least one 6-membered carbon ring; R" is a group having a photosensitive group containing a carbon-carbon double bond dimerizable and polymerizable by chemical rays; R''' is arbitrarily selected from OH or O<-> R* (R* is an ammonium ion containing a carbon-carbon double bond dimerizable and polymerizable by chemical rays)], and a sensitizer or a photoinitiator (e.g. Michler's ketone or a benzoin ether) as solutes in a solvent (e.g. a non-protonic polar solvent or an ether-based compound).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photosensitive polyimide precursor solution, a heat-resistant polyimide coating film obtained therefrom, and a method for producing the same. It forms a polyimide.

[0002]

2. Description of the Related Art Polyimide is useful for application in the field of electronics, and is used as an insulating film material or a protective coating material on semiconductor devices. In particular, wholly aromatic polyimides have greatly contributed to higher densities, multifunctionality, and the like in flexible circuit boards and integrated circuits because of their excellent heat resistance, mechanical properties, and electrical properties. In the case of forming an interlayer insulating film or a protective film of a fine circuit such as a flexible circuit board or an integrated circuit, a polyimide precursor solution has been conventionally used. As such a polyimide precursor solution, a polyamic acid solution containing a polyamic acid represented by the following general formula as a solute is known.

[0003]

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In the above-mentioned applications, it is usually necessary to make a hole in the insulating film for conduction between the upper and lower conductor layers of the insulating film or conduction with external leads. That is, a heat-resistant organic substance such as polyimide has not been used in a uniform film state, but has been used as a relief structure having holes. For example, Epifano and Jordan (German Offenlegungsschrift 1, 764, 977) form a positive resist on a layer of a soluble polyimide precursor (polyamic acid) and then form a pattern by the usual chemical techniques. Then, the polyimide precursor in the portion where the resist disappeared was eluted, the resist portion was peeled off, and heat treatment was performed to obtain a polyimide relief pattern. Also, Jones
(J.Plymer Sci. Part C, 22, 773, 1969) and Agnihotri
(Proc.SPEReginal Tech.Conf. 74,1976) forms a photoresist pattern on a polyimide layer, using hydrazine and ethylenediamine as etchants, respectively.
A polyimide relief pattern was obtained.

[0005] These methods for indirectly forming a relief pattern have been complicated because they require two extra steps, namely, formation of a photoresist film and stripping thereof. In these methods, the polyimide layer or the polyimide precursor layer has the same solubility in the etching solution as a whole, and the boundary between the dissolved portion and the remaining portion is likely to be unclear. These problems can be easily solved by a method of forming a relief pattern made of a heat-resistant organic material directly using a heat-resistant photoresist, but known general photoresists have a limit in terms of heat resistance. .

As heat resistant photoresists, Kevwin and Go
ldrick (Polymer Eng. & Sci. 11, 426, 1971) has found a system consisting of a polyimide precursor and dichromic acid. Because of the photosensitivity of this system, it can be used directly to make relief patterns using conventional photochemical techniques. In addition, since the polyimide precursor itself forming the relief pattern generates a soluble portion and an insoluble portion by pattern exposure, the boundary between the dissolved portion and the remaining portion becomes clear. However, this system is extremely poor in stability and must be used immediately after mixing the polyimide precursor and the dichromate, which is a great limitation for industrial applications. Further, this system is not suitable for semiconductor applications in which the presence of inorganic ions adversely affects reliability because inorganic ions are present in the crosslinked layer. Another example of a heat resistant photoresist is Kleeberg (USP 3,957,512, USP 4,040,831)
The following structural formula disclosed by

[0007]

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As shown in the above, there is a polyimide precursor in which a photosensitive group is introduced by an ester group. This polymer is obtained mainly by reacting a compound having a photosensitive group and a diacid chloride group with a diamine. However, a problem in this system is that the production of the polyimide precursor solution is complicated. That is, in producing a compound having a photosensitive group and a diacid chloride group, a compound having a photosensitive group and a carboxylic acid is first formed from a dianhydride and an alcohol having a photosensitive group, and then an acid chloride is formed. Further, a compound having a photosensitive group and a diacid chloride group is reacted with a diamine to obtain a precursor solution. In this system, chlorine ions generated by dehydrochlorination remain in the resist as it is, which may adversely affect reliability in semiconductor applications, and is not preferable in this respect.

In addition, Hiramoto (JP-B-59-52822 and JP-B-59-52823) discloses that a polyimide precursor (polyamic acid) solution is added with an amine having a photosensitive group to impart photosensitivity. A technique for introducing a photosensitive group into a polyimide precursor (polyamic acid) via an amide bond to impart photosensitivity is disclosed. According to this technique, a photosensitive polyimide precursor solution containing no inorganic salt or inorganic ion that has an adverse effect on reliability in semiconductor applications can be obtained. Each of these photosensitive polyimide precursor solutions, including Hiramoto, is a solution of a polymer having a high degree of polymerization. When obtaining a polyimide coating from these polymer solutions, generally, this polymer solution is coated on a substrate such as copper, glass, etc., and the solvent is removed and imidation is performed by heating to obtain a polyimide coating. .

However, when coating these polymer solutions having a high degree of polymerization, if the degree of polymerization of the polymer is high, the concentration of the solute must be lowered in order to make the viscosity of the solution coatable. On the contrary, if the concentration of the solute is increased in order to increase the productivity, there is a problem that the viscosity of the solution becomes high and coating becomes impossible. That is, since these solutions have a high viscosity, it is necessary to lower the solute concentration and lower the viscosity in order to apply the solution to the spin coating method, which is a coating method often used in semiconductor applications. As a result, coating by the spin coating method was possible, but the film thickness obtained by one coating was thin, and the productivity was low. Further, even if the coating can be performed, there is a problem that a coating film or a film having excellent mechanical and thermal properties cannot be obtained. Further, the polymer solution is hard to withstand long-term storage, and it has been extremely difficult to store the polymer solution for a long time while maintaining its degree of polymerization.

[0011]

SUMMARY OF THE INVENTION In view of the above situation, an object of the present invention is to provide a photosensitive polyimide precursor solution which is easy to manufacture, contains no inorganic salts or inorganic ions, has a high concentration and a low viscosity, and An object of the present invention is to provide a heat-resistant polyimide coating film obtained and a method for producing the same.

[0012]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, if a specific monomer is first combined, it is possible to obtain a good solution from a solution containing the monomer even if it is not a polymer. It has been found that a polyimide coating film having physical properties can be obtained. That is, a polyimide precursor solution containing a salt obtained from a specific compound having an amino group and a specific compound having a carboxyl group as a solute, despite containing a high concentration of a salt of a monomer. It has been found that a low-viscosity, high-strength polyimide coating film or film can be obtained from this solution.Based on these findings, no polymer was used as a polyimide precursor, and a high concentration and low concentration were obtained. A technique relating to a polyimide precursor solution having a viscosity was developed (Japanese Patent Application No. 9-165557). Further, it has been found that a photosensitive polyimide precursor solution can be obtained by using a compound having a photosensitive group represented by the following general formula (2) instead of the compound having a carboxyl group. The invention has been reached.

That is, the gist of the present invention is that first, a compound having an amino group represented by the general formula (1) and a compound represented by the general formula (2)
A photosensitive polyimide precursor solution, comprising a salt of the compound shown in (1) and a sensitizer or a photoinitiator dissolved as a solute in a solvent.

[0014]

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[In the general formula (1), R represents a divalent aromatic residue having at least one carbon 6-membered ring. In the general formula (2), R ′ represents a tetravalent aromatic residue containing at least one carbon 6-membered ring, and four carbonyl groups are directly linked to different carbon atoms in the residue; Two of the four are paired and are attached to adjacent carbon atoms in the six-membered carbon ring and R ″ is a photosensitive moiety containing a carbon-carbon double bond that can be dimerized or polymerized by actinic radiation. R ′ ″ is a hydroxyl group and —O ^— R ^* (R ^* is an ammonium ion containing a carbon-carbon double bond that can be dimerized or polymerized by actinic radiation). It is arbitrarily selected from the groups having. ]

Second, there is a polyimide coating film obtained from the photosensitive polyimide precursor solution. Thirdly, there is provided a method for producing a polyimide coating film, which comprises applying the photosensitive polyimide precursor solution on a substrate and heating the solution to imidize the substrate. Fourthly, there is provided a method for producing a polyimide coating film on which a relief pattern is formed, which comprises applying the photosensitive polyimide precursor solution onto a substrate, exposing, developing, and heat-imidizing.

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. First, terms used in the present invention will be described. (1) Salt A complex obtained by mixing a compound having an amino group and a compound having a carboxyl group or a derivative thereof in a solvent, and the complex can bind in any state (ionic bond or nonionic bond). May be. (2) Polyimide 80% by mole or more of the repeating unit of the polymer chain has an imide structure. Generally, this organic polymer has no melting point or softening point at 400 ° C. or lower.

(3) Polyimide Precursor An organic compound which becomes a polyimide by ring closure by heating or chemical action. Here, ring closure means that an imide ring is formed. (4) Polyimide precursor solution The polyimide precursor is dissolved in a solvent. Here, the solvent refers to a compound which is liquid at 25 ° C. (5) Viscosity The rotational viscosity at 20 ° C. was measured using a DVL-BII type digital viscometer (B type viscometer) manufactured by Tokimec Co., Ltd. (6) Solute concentration It is a numerical value expressing the weight ratio of the polyimide precursor in the solution in percentage.

(7) Polyimide coating film A polyimide film formed on a base material such as copper, aluminum, glass, etc. What is called a coating and what is used after being peeled off from the substrate is called a polyimide film.

Further, the present invention will be described. The photosensitive polyimide precursor solution of the present invention comprises a salt of a compound having an amino group represented by the general formula (1) and a compound represented by the general formula (2), and a sensitizer or a photoinitiator as a solute in a solvent. Are dissolved in In the compound having an amino group represented by the general formula (1), R represents at least one carbon 6
It represents a divalent aromatic residue having a membered ring, and specific examples of R include the following.

[0021]

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[0022]

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Particularly, R is preferably the following.

[0024]

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In the compound represented by the general formula (2), R ′
Represents a tetravalent aromatic residue containing at least one 6-membered carbon ring, four carbonyl groups are directly linked to different carbon atoms in the residue, and two of the four are paired. Wherein R ″ is a carbon-dimerizable or polymerizable by actinic radiation.
A photosensitive group containing a carbon double bond, wherein R ″ ′ is a hydroxyl group and —O ^— R ^* (R ^* is an ammonium ion containing a carbon-carbon double bond that can be dimerized or polymerized by actinic radiation) Arbitrarily selected from the groups having photosensitivity. In the compound represented by the general formula (2), specific examples of R ′ include the following.

[0026]

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Particularly, R 'is preferably as follows.

[0028]

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Specific examples of R ″ include the following:

[0030]

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The following are particularly preferred as R ″.

[0032]

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Specific examples of R '''include the following:

[0034]

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The following are particularly preferred as R ′ ″.

[0036]

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As a sensitizer or a photoinitiator, J. Kosa
r "Light Sensitive Systems" (John Wiley & Son
s, Inc. New York 1965), p143-p146 and p160-p188. Preferred examples include Michler's ketone, benzoin ether, 2-ter
t-butyl-9,10-anthraquinone and 4,4′-bis (diethylamino) benzophenone.

The polyimide precursor solution of the present invention has -30
A diester of a tetracarboxylic acid having a skeleton of R ′ in the general formula (2) and a hydroxy compound having an R ″ group in a solvent at ６０60 ° C., having an amino group having a skeleton of R in the general formula (1) It can be obtained by dissolving a compound and a sensitizer or a photoinitiator, or by further dissolving an amine compound which is a source of an R ^* group in the general formula (2). Then, a salt of the compound having an amino group represented by the general formula (1) and the compound represented by the general formula (2), and a sensitizer or a photoinitiator are dissolved in a solvent as solutes. As the solvent, any solvent can be used as long as it dissolves a compound having an amino group represented by the general formula (1), a salt of the compound represented by the general formula (2), and a sensitizer or a photoinitiator. .

Examples of the solvent include aprotic polar solvents, ether compounds and water-soluble alcohol compounds. Examples of aprotic polar solvents include N-methylpyrrolidone, N, N-dimethylformamide, N, N
-Dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, and the like, and examples of the ether compound include 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ethoxyethanol, 2-isopropoxyethanol, and 2-isopropoxyethanol. Butoxyethanol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monoethyl ether, tetraethylene glycol, 1-methoxy-2-propanol, 1-ethoxy- 2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipro Glycol monoethyl ether, tripropylene glycol monomethyl ether, polyethylene glycol, polypropylene glycol, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and the like.

Examples of the water-soluble alcohol compound include methanol, ethanol, 1-propanol, 2-propanol, tert-butyl alcohol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,3-butane. Diol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-butene-1,4-diol, 2-methyl-2,
Examples thereof include 4-pentanediol, 1,2,6-hexanetriol, and diacetone alcohol. The above compounds can be used alone or in combination of two or more. Particularly preferred examples of these solvents include N, N-dimethylformamide, N, N-
Dimethylacetamide, 2-methoxyethanol, diethylene glycol monomethyl ether, 1-methoxy-
2-propanol and the like, and the mixed solvent is N 2
-Methylpyrrolidone and diethylene glycol monomethyl ether; N-methylpyrrolidone and methanol; and N-methylpyrrolidone and 2-methoxyethanol in combination.

Further, an amine compound can be used as a solvent, and an amine compound alone or a mixture of the above-described various solvents and an amine compound can also be used.
In this case, any amine compound may be used, but a tertiary amine is preferably used. Among these, it is particularly preferable to use triethylamine and dimethylaminoethanol.

The solid concentration of the polyimide precursor in the polyimide precursor solution in the present invention is preferably 30% by weight or more. It is more preferably at least 35% by weight, even more preferably at least 40% by weight. If the amount is less than 30% by weight, the effect of increasing the productivity during coating may be reduced. The viscosity of the polyimide precursor solution is preferably 100 poise or less, more preferably 85 poise or less, and even more preferably 60 poise or less. If it exceeds 100 poise, coating may become difficult.

In the photosensitive polyimide precursor solution of the present invention, a part of the compound represented by the general formula (2) is replaced with a compound having a carboxyl group represented by the general formula (3) or a dicarboxylic acid represented by the general formula (4). It may be replaced with an anhydride. In this case, the polyimide obtained by controlling the molar ratio of the compound having a carboxyl group represented by the general formula (3) or the dicarboxylic anhydride represented by the general formula (4) to the compound represented by the general formula (2) Fluidity can be controlled. At this time, the molar ratio of the compound represented by the general formula (2) to the compound having a carboxyl group represented by the general formula (3) or the dicarboxylic anhydride represented by the general formula (4) is preferably 100: 0 to 100: 20. , 100:
0-100: 11 is more preferred. When the molar ratio of the compound having a carboxyl group represented by the general formula (3) or the dicarboxylic anhydride represented by the general formula (4) to the compound 100 represented by the general formula (2) exceeds 20, only a polyimide film having low strength can be obtained. There may not be.

[0044]

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Further, a part of the compound represented by the general formula (2) may be replaced with a tetracarboxylic dianhydride represented by the general formula (5). At this time, the compound 1 represented by the general formula (2)
The molar ratio of the tetracarboxylic dianhydride represented by the general formula (5) to 00 is preferably from 0 to 30. By adjusting this ratio, the viscosity of the polyimide precursor solution can be finely adjusted. When the molar ratio of the tetracarboxylic dianhydride shown in the general formula (5) to the compound 100 in the general formula (2) exceeds 100, a low-viscosity polyimide precursor solution which is a feature of the present invention cannot be obtained. is there.

[0046]

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Further, when a part of the diamine represented by the general formula (1) is replaced with the amine represented by the general formula (6),
The melt fluidity of the obtained polyimide can be controlled. In this case, the ratio of the diamine represented by the general formula (1) to the amine represented by the general formula (6) is preferably 100: 0 to 100: 20, and more preferably 100: 0 to 100: 11. If the molar ratio of the amine represented by the general formula (6) to the diamine 100 represented by the general formula (1) exceeds 20, a high-strength polyimide film may not be obtained.

[0048]

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Further, the polyimide precursor solution of the present invention may contain, if necessary, for example, vinylethoxysilane, vinylmethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Aminopropyltrimethoxysilane, γ
-Addition of an organic silane compound such as aminopropyltriethoxysilane, hexamethyldisilazane or the like as an adhesion aid, or other known additives such as pigments, fillers, abrasives, dielectrics, lubricants, etc. Can be added in a range that does not impair. In addition, other polymers and solvents such as water-insoluble ethers, alcohols, ketones, esters, halogenated hydrocarbons, hydrocarbons and the like can be added within a range not to impair the effects of the present invention.

The polyimide coating film can be obtained by applying a photosensitive polyimide precursor solution on a substrate by a method described later and heating it to imidize it. Further, the polyimide coating film on which the relief pattern is formed is manufactured by a commonly used photoresist technique. That is, the photosensitive polyimide precursor solution obtained as described above,
Conventionally known spin coating method, spray coating method or the like, extrusion from a slit-shaped nozzle, coating on a substrate with a bar coater or the like to remove the solvent, placing a negative mask on the obtained coating film, chemical Expose by irradiating a line. Examples of the actinic radiation include X-rays, electron beams, ultraviolet rays, visible rays, and the like, and are preferably ultraviolet rays. Then
A relief structure is obtained by dissolving and removing the unexposed portion with a developer. The developer needs to be appropriately selected according to the polyimide structure. As the developer, a mixed solvent of an aprotic polar solvent such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and hexamethylphosphoramide and an alcohol such as methanol, ethanol, and isopropanol is generally used. After development, the resulting pattern is imidized by heating to obtain a patterned polyimide coating film. In the polyimide coating film including the patterned polyimide coating film, one that is used while being in close contact with the substrate is called a polyimide coating, and one that is peeled off from the substrate and used is called a polyimide film.

The imidization conditions at this time are 200 to 400.
C. is preferable, and 250 to 350 C. is more preferable. 20
If the temperature is outside the range of 0 to 400 ° C., imidization may be insufficient, or the coating may be deformed or deteriorated by heat.

By using the photosensitive polyimide precursor solution of the present invention, excellent heat resistance, chemical resistance, insulation properties,
A pattern having mechanical characteristics and high resolution can be obtained. Further, the polyimide pattern does not include an inorganic salt or an inorganic ion that adversely affects the semiconductor.
Furthermore, the photosensitive polyimide precursor solution of the present invention is easier to produce, has a higher concentration, has better storage stability, and thus greatly contributes to an improvement in productivity, as compared with the conventional photosensitive polyimide precursor solution. is there.

The photosensitive polyimide precursor solution of the present invention and the polyimide coating film obtained therefrom are used for the following. For example, a passivation film of a semiconductor, an insulating film in a multilayer wiring of an integrated circuit, an ion implantation protection film of an integrated circuit, a solder dam at the time of soldering, a resin for filling an isolation groove of an integrated circuit, and a fine pattern of an integrated circuit are used. It is used for forming a lift-off material for a lift-off method and a soldering protective film for a printed circuit.
Further, it can be applied to a metal deposition or a dry etching process as a heat resistant photoresist. further,
It can also be applied to general photoresist applications utilizing features such as chemical resistance.

[0054]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. In Examples, ODP-HEMA refers to a diester of oxydiphthalic acid and hydroxyethyl methacrylate, and BPA-HEMA refers to a diester of biphenyltetracarboxylic acid and hydroxyethyl methacrylate, which are disclosed in JP-A-6-305929. And M. Farahani et al. (J. Dent. Res. 67, January, 1991)
And the production was confirmed by NMR.

Example 1 ODP-HEMA (14.3 g, 25.07 mmol) was dissolved in dimethylformamide (45.0 g).
5.02 g of 4'-oxydianiline (25.07 mmol
l) was added. After stirring for one hour, Michler's ketone 0.1.
632 g (2.36 mmol) was added and the mixture was further stirred for 3 hours to obtain a bluish-yellow transparent solution having a viscosity of 0.054 poise. (Polyimide precursor-equivalent solid content of 30% by weight) The obtained solution was spin-coated on a glass plate by 10%.
It was applied to a thickness of μm. A mask on a slit was placed on the coating film, and the film was exposed to a high-pressure mercury lamp of 500 mW for 10 minutes. After exposure, development was performed with a mixed solvent of dimethylacetamide (1 mol) and isopropanol (2 mol) to obtain a relief pattern. This was heated at 300 ° C. for 30 minutes to obtain a polyimide pattern.

Example 2 14.3 g (25.07 mmol) of ODP-HEMA was dissolved in 39.3 g of dimethylformamide.
5.02 g of 4'-oxydianiline (25.07 mmol
l) was added. After stirring for 1 hour, 5.7 g (36.23 g) of dimethylamino methacrylate and 0.68 g (2.53 mmol) of Michler's ketone were added, and the mixture was further stirred for 3 hours to obtain a bluish-yellow transparent solution having a viscosity of 0.08 poise. Obtained. (Solid content in terms of polyimide precursor: 50% by weight) The obtained solution was applied, exposed and developed in the same manner as in Example 1 to obtain a polyimide pattern.

Example 3 25.0 g (45.09 mmol) of BPA-HEMA was dissolved in 14.58 g of dimethylformamide, and 9.03 g of 3,4'-oxydianiline (45.09 m) was added thereto.
mol) was added. After stirring for 1 hour, 1.57 g (5.86 mmol) of Michler's ketone was added, and the mixture was further stirred for 3 hours. As a result, a bluish yellow transparent solution having a viscosity of 58 poise was obtained. (Polyimide equivalent solid content of 7
(0% by weight) The obtained solution was coated, exposed and developed in the same manner as in Example 1 to obtain a polyimide pattern.

[0058]

As described above, the photosensitive polyimide precursor solution of the present invention is easy to produce, does not contain inorganic salts or inorganic ions, has a high concentration and a low viscosity. Thus, a heat-resistant polyimide coating film or a polyimide coating film having a relief pattern formed thereon can be obtained. According to the production method of the present invention, a polyimide coating film can be easily produced.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/07 C08K 5/07 C09D 179/08 C09D 179/08 Z G03F 7/028 G03F 7/028 7/038 504 7/038 504 // C08J 7/00 301 C08J 7/00 301 302 302 302 (72) Inventor Yoshiaki Echigo 23 Uji Kozakura, Uji City, Kyoto Prefecture Unitika Research Laboratory

Claims (5)

[Claims] 1. A solvent comprising a salt of a compound having an amino group represented by the general formula (1) and a compound represented by the general formula (2), and a sensitizer or a photoinitiator dissolved in a solvent as a solute. A photosensitive polyimide precursor solution, characterized in that: Embedded image [In the general formula (1), R represents a divalent aromatic residue having at least one carbon 6-membered ring. In the general formula (2), R ′
Represents a tetravalent aromatic residue containing at least one 6-membered carbon ring, four carbonyl groups are directly linked to different carbon atoms in the residue, and two of the four are paired. Wherein R ″ is a carbon-dimerizable or polymerizable by actinic radiation.
A group having a photosensitive group containing a carbon double bond;
Is arbitrarily selected from a hydroxyl group and a photosensitive group represented by —O ^— R ^* (R ^* is an ammonium ion containing a carbon-carbon double bond that can be dimerized or polymerized by actinic radiation). ] 2. The method according to claim 1, wherein R, R ′, R ″ and R ″ ″ in the general formulas (1) and (2) are each selected from the following. 2. The photosensitive polyimide precursor solution according to 1. Embedded image 3. A polyimide coating film obtained from the photosensitive polyimide precursor solution according to claim 1. 4. A method for producing a polyimide coating film, comprising applying the photosensitive polyimide precursor solution according to claim 1 onto a substrate, and heating to imidize the substrate. 5. A method for producing a polyimide film having a relief pattern formed thereon, comprising applying the photosensitive polyimide precursor solution according to claim 1 onto a substrate, exposing, developing, and heat imidizing. Method.