JP3365096B2 - Pattern forming method using photosensitive polyamide - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel aromatic polyamide having excellent solubility in an aqueous alkaline solution and containing a photosensitive group and an acidic group in a polymer chain, more specifically, heat resistance, electrical properties, mechanical properties. The present invention relates to a photosensitive polyamide soluble in an alkaline aqueous solution, which is excellent in physical properties and transparency and is suitable as a base polymer material for a color filter. Further, the present invention can be preferably used for applications such as a material for forming an insulating film or a passivation film for a solid element in the semiconductor industry, an interlayer insulating material for a semiconductor integrated circuit, a multilayer printed wiring board, or the like.

Liquid crystal elements and electroluminescence (E
In a display device such as the L) element or the like, heat resistance of the color filter is required to form a low-resistance transparent electrode (indium tin oxide or the like) on the surface of the color filter. Further, if the base polymer itself, which is the base material of the color filter, is colored, the transmittance of light of a specific wavelength becomes poor. In addition, the insulating property of the color filter is required for the use of a specific electrode configuration. Further, the color filter needs to be formed by patterning each color of R (red), G (green), and B (blue) for each pixel. Recently, as the density of the display becomes higher, the pixel size becomes smaller. Is becoming more pronounced. Therefore, the base polymer used as the base material of the color filter is required to have heat resistance, colorless transparency, and insulating properties, and at the same time, to have photosensitivity. In addition, in the semiconductor industry, it is required to have excellent heat resistance and insulation properties for the use as a material for forming an insulating film or a passivation film for a solid element and an interlayer insulating material such as a semiconductor integrated circuit or a multilayer printed wiring board. In addition, a photosensitive heat-resistant material is required due to the demand for higher density.

[Description of Prior Art]

Conventionally, there have been many reports on photosensitive polyamides, but most of them are based on the combination of a polyamide containing no photosensitive group and a photopolymerizable unsaturated compound (monomer). There was not (JP-A-48
-89004, JP-A-49-74739 and JP-A-56.
-93794 etc.). Polyamides containing a photosensitive group have also been proposed (JP-A-50-8605 and JP-A-5-5605).
6-122833) are all aliphatic polyamides and have insufficient heat resistance and photosensitivity.

As a means for solving such problems,
JP-A-60-6725, JP-A-60-12462
4 discloses an aromatic polyamide having a photosensitive group in its side chain. However, when a pattern is formed using this aromatic polyamide, the development must be performed in an organic solvent system, so that special consideration is required in the process. Further, the photosensitive polyamic acid (precursor of polyimide) can be developed with an alkaline aqueous solution, but when heated, it imidizes, so that there is a problem that distortion or stress occurs due to contraction. Further, polyimide is usually colored yellow and has a low transmittance on the short wavelength side in the visible light wavelength region, and is not suitable for color filter applications.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, in which a solution of a photosensitive polyamide is used to develop a substantially aqueous solution to obtain heat resistance, It is an object of the present invention to provide a method for forming a pattern of a polyamide film having excellent insulation properties and colorless transparency.

[0006]

The present invention SUMMARY OF THE INVENTION The aromatic diamine compound H ₂ N-R ₁ -NH ₂ with a photosensitive group represented by the following following general formula (I) (I) (In the formula R ₁ represents a residue of an aromatic group containing a photosensitive group.) 100 to 10 mol% and the following general formula (II)
Aromatic diamine compound H ₂ N—R ₂ —NH ₂ (II) containing no photosensitive group represented by the formula (wherein R ₂ represents a residue of an aromatic group containing no photosensitive group) 0 to A photosensitive polyamide comprising a copolycondensate of 90 mol% of an aromatic amine component, 100 to 10 mol% of an aromatic tricarboxylic acid compound and 0 to 90 mol% of an aromatic dicarboxylic acid compound. The solution is used to form a polyamide film, and the polyamide film is exposed in a predetermined pattern and then developed with an aqueous solution containing a basic compound to give a thickness not containing a coloring material.
400-700 measured on a 1.5 μm exposed coating
Has transparency with a transmittance of 90% or more in nm
The present invention relates to a pattern forming method characterized by forming a pattern of a polyamide film .

[0007]

The present invention will be described in detail below. The photosensitive polyamide used in the present invention is a polyamide composed of a copolycondensate of an aromatic amine component and an aromatic carboxylic acid component. That is, the photosensitive polyamide used in the present invention is obtained by polycondensation or copolycondensation of an aromatic amine compound and an aromatic carboxylic acid compound (the polycondensation product is generally used as an aromatic diamine component). Formula (I)
It can be obtained when the tricarboxylic acid compound is used as the aromatic carboxylic acid component by using the diamine compound of. ).

The aromatic amine component is an aromatic diamine compound 100 to 10 having a photosensitive group represented by the general formula (I).
Mol% and an aromatic diamine compound having no photosensitive group represented by the general formula (II) in an amount of 0 to 90 mol%. The component of general formula (I) is an essential component because it imparts photosensitivity to polyamide. Further, the general formula (II) component serves to improve the thermal properties of the polyamide, but the object of the present invention can be achieved even if it is not contained at all. Further, preferably, the content of the general formula (II) component is 0 to 40 mol% with respect to 100 to 60% of the general formula (I) component. General formula (I
This is because if the amount of component (I) is too large, the concentration of photosensitive groups in the copolymer will decrease and the photosensitivity will decrease, which is not preferable.

The aromatic diamine compound represented by the general formula (I) may be any aromatic diamine having a photosensitive hydrocarbon group, for example, 3,5-diaminobenzoic acid ethyl acrylate ester, 2,4-diaminobenzoic acid ethyl acrylate, 3,5-diaminobenzoic acid ethyl methacrylic acid ester, 2,4-diaminobenzoic acid ethyl methacrylic acid ester, 3,5-diaminobenzoic acid glycidyl acrylate ester, 2 , 4
-Diaminobenzoic acid glycidyl acrylate ester,
Benzoic acid esters such as 3,5-diaminobenzoic acid glycidyl methacrylate ester, 2,4-diaminobenzoic acid glycidyl methacrylate ester, 3,5-diaminobenzoic acid cinnamate ester, and 2,4-diaminobenzoic acid cinnamate ester , Benzyl acrylates such as 3,5-diaminobenzyl acrylate and 3,5-diaminobenzyl methacrylate, 4-acrylamido-3,4'-diaminodiphenyl ether, 2-acrylamido-3,4'-diaminodiphenyl ether, 4
-Cinnamamide-3,4'-diaminodiphenyl ether, 3,4'-diacrylamide-3 ', 4-diaminodiphenyl ether, 3,4'-dicinnamamide-
3 ', 4-diaminodiphenyl ether, 4-methyl-
2'-carboxyethyl methacrylate-3,
4'-diaminodiphenyl ether [carboxyethyl methacrylate _{ester, CH 2 = C (CH 3} ) COO
CH ₂ CH ₂ OOC-], 4-methyl-2′-carboxyethyl acrylic acid ester-3,4′-diaminodiphenyl ether [carboxyethyl acrylic acid ester is CH ₂ = CHCOOCH ₂ CH ₂ OOC-], and the like diphenyl ethers. , And 4,4′-diaminochalcone, 3,3′-diaminochalcone, 3,4′-diaminochalcone, 3 ′, 4-diaminochalcone, 4′-methyl-3 ′, 4-diaminochalcone, 4′- Methoxy-
3 ', 4-diaminochalcone, 3'-methyl-3,5-
Examples thereof include diaminochalcone.

Specific examples of the diamine compound represented by the general formula (II) having no photosensitive group include paraphenylenediamine, metaphenylenediamine, 2,4-diaminotoluene and 4,4. '-Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, o-toluidine, 1,4-bis (4-aminophenoxy) benzene, 2,2'-bis (4-aminophenoxyphenyl) propane, o-toluidine sulfone, etc. Can be mentioned.

The aromatic diamine compound represented by the general formula (I) may be used in combination of two or more, if necessary.
Two or more kinds of the aromatic diamine compounds represented by the general formula (II) used in combination can be used in combination, if necessary.

The aromatic carboxylic acid component comprises 100 to 10 mol% of aromatic tricarboxylic acid component and 0 to 90 mol% of aromatic dicarboxylic acid component. Preferably, the aromatic dicarboxylic acid component is 0 to 60 mol% based on 100 to 40 mol% of the aromatic tricarboxylic acid component. This is because the aromatic tricarboxylic acid component is a component that imparts alkali water solubility in the present invention, and if it is too small, it cannot be developed with an alkaline aqueous solution. Here, of the three carboxyl groups of the aromatic tricarboxylic acid component, two are involved in the amide bond, and the remaining one carboxyl group imparts alkali water solubility to the polyamide. This residual carboxyl group may be present in the polyamide in the form of being partially imidized or subjected to other reactions in the polyamide synthesis step described below and the subsequent treatment. However, at the time of development, at least 1 of the aromatic carboxylic acid component monomer units present in the polymer is
It is preferable that 0% or more of a carboxyl group (the carboxyl group may be modified into a group soluble in an aqueous solution containing a basic compound, for example, a group such as a carboxylic acid halide) may be present. To be able to develop easily,
It is particularly preferred that 40% or more of the carboxyl groups are present.

Examples of the aromatic tricarboxylic acid component include aromatic tricarboxylic acids, their anhydrides and their acid halides. Specifically, trimellitic acid or its anhydride, 3,3 ', 4-tricarboxyl. -Biphenyl or its anhydride, trimellitic anhydride chloride,

[0015]

[Chemical 1]

And the like. Among these, acid halides of aromatic tricarboxylic acids, particularly those containing a monoanhydride group and a halogenated group such as trimellitic anhydride chloride are preferable.

The photosensitive polyamide used in the present invention is polyamide 0.5 g / N-methyl-2-pyrrolidone 100 m.
It is preferable that the solution having a concentration of 1 has a logarithmic viscosity measured at 30 ° C. of 0.1 to 1.5, particularly 0.2 to 1.0.

The production of the photosensitive polyamide used in the present invention will be described in more detail. The above polycondensate (copolycondensate) is used.
The use ratio of the aromatic carboxylic acid component and the two kinds of aromatic diamine components represented by the general formulas (I) and (II) in synthesizing is approximately equimolar. These synthetic reactions are preferably carried out at a relatively low temperature. That is, it is preferable to carry out the polymerization reaction in an organic solvent at a reaction temperature of 100 ° C. or lower for 0.1 to 48 hours, and as a result, the copolycondensate is synthesized to obtain the polyamide used in the present invention.

Examples of the organic solvent in the above reaction include N, N-dimethylsulfoxide, N, N-dimethylformamide, N, N-diethylformamide, N, N.
-Dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, hexamethylenephosphoamide and the like.

Next, the procedure for forming the pattern of the present invention will be described. First, the photosensitive polyamide obtained above is dissolved in an organic solvent, and a polyamide solution (photosensitive composition) to which a photopolymerization initiator and other additives are further added is prepared. As the organic solvent used here, the organic solvent used in the above reaction can be used.

The photopolymerization initiator to be blended is, for example, a bisazide compound, Michler's ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10. -Anthraquinone, benzyl, anisyl, 4,4'-bis (diethylamino) benzophenone, acetophenone, benzophenone, 1,5-acenaphthene, thioxanthone or its derivatives, triazine derivative, p-dimethylaminobenzoic acid ethyl ester,
Examples thereof include photopolymerization initiators such as morpholino derivatives such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1.

Examples of the bisazide compound used as the photopolymerization initiator include, for example, 4,4'-diazidochalcone, 4,4'-diazidobenzalacetone, 2,6-di- (4'- Preferred examples thereof include azidobenzal) methylcyclohexanone and 4,4′-diazidostilbene. Further, examples of the thioxanthones used as the photopolymerization initiator include 2,4-diethylthioxanthone and 2-chlorothioxanthone.

The amount of the photopolymerization initiator blended is 100 parts by weight of the photosensitive resin such as the photosensitive polyamide.
The amount is preferably 0.2 to 40 parts by weight, particularly 0.5 to 30 parts by weight. If the blending amount is too small, the sensitivity of the resulting composition will be low, and if it is too large, the heat resistance of the photocured film (relief pattern) formed by the resulting composition will be lowered, which is not preferable.

Other additives include, for example, an adhesion improver between the photosensitive film and the substrate, a thermal polymerization inhibitor and the like.

When forming a colored pattern, a photosensitive polyamide is dissolved in an organic solvent, and a coloring material is further added in addition to a photopolymerization initiator and other additives to prepare a polyamide solution (photosensitive Composition) is prepared. The coloring material used here may be an inorganic or organic dye or an inorganic or organic pigment. Organic pigments are most preferable for color filter applications from the viewpoint of color tone and durability. As the organic pigment, those having good transparency and excellent heat resistance, light resistance and solvent resistance are preferable, and examples thereof include azo chelate type, condensed azo type, phthalocyanine type, benzimidazolone type and quinacridone. , Isoindolinone, pyranthrone, dibromanthanthrone, indanthrone, anthrapyrimidine, flavanthrone, perylene, perinone, quinophthalone, thioindigo, dioxazine, anthraquinone, etc. And one or more of them can be appropriately selected and used.
It is preferable to use the organic pigment having a particle diameter of 1 μm or less from the viewpoints of light transmittance, film surface uniformity, and the like.

The organic pigment must be sufficiently dispersed in the photosensitive composition. For example, the photosensitive composition should be prepared by a dispersion method such as a ball mill method, a roll method or an ultrasonic method. You can

The photosensitive composition thus obtained is
For example, the solution is coated on a substrate at a temperature of 0 to 60 ° C. and dried at a temperature of 180 ° C. or less to form a coating film (dry film) of the composition, and then a pattern mask is formed on the coating film. By irradiating parallel rays of an ultra-high pressure mercury lamp through the film to photo-cure the coating film in a pattern, and then immersing it in a developing solution to form an unexposed part (uncured part) of the photo-cured film (relief pattern). The relief pattern can be formed on the substrate by performing development for eluting and removing.

The solution of the photosensitive composition can be applied to the surface of the substrate by a method such as a spin coating method, a roll coating method, a dipping method and a spraying method. Among these, a coating method such as a spin coating method is preferable because uniform coating can be performed. The spin coating method usually has a rotation speed of 1
It is performed at 00 to 10000 rpm (rotation / minute). Practically, it is preferably 300 to 5000 rpm, more preferably 500 to 4000 rpm. The coating film is dried at 180 ° C. with a hot air dryer, a hot plate or the like.
Hereinafter, it is preferable to perform the treatment at a temperature of 50 to 150 ° C. for 1 to 60 minutes, particularly 2 to 30 minutes to substantially remove the organic solvent to form a photosensitive thin film (coating film). The drying may be performed under reduced pressure.

The thickness of the coating film (film after drying) made of the above photosensitive resin composition is usually about 0.1-10.
It is preferably 0 μm, and particularly preferably about 0.2 to 5.0 μm.

The developer used in the present invention is substantially an aqueous solution and contains a basic compound. That is, it contains a basic compound and contains water in a volume fraction of 30% or more, preferably 50% or more, more preferably 60% or more. The developing solution may contain an organic solvent that can be mixed with water, and particularly may contain an organic solvent that improves the wettability with the coating film (film after drying) made of the photosensitive composition. . Specifically, methanol, alcohols such as ethanol, polyhydric alcohols such as diethylene glycol, triethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, monoalkyl ethers of polyhydric alcohols such as diethylene glycol monomethyl ether, Examples thereof include ketones such as acetone and methyl ethyl ketone.

As the alkaline substance used in the developing solution, an inorganic base or an organic base can be used, and specifically, an alkali metal or an alkaline earth metal such as sodium hydroxide, potassium hydroxide or magnesium hydroxide can be used. Examples thereof include hydroxides, salts of alkali metals or alkaline earth metals such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and magnesium carbonate, and alkyl-substituted ammonium hydroxide or ammonium hydroxide. Among these, preferred are the alkyl substitution products of sodium carbonate and ammonium hydroxide, and particularly the alkyl substitution products of ammonium hydroxide are those in which 1 to 4 lower alkyls having 1 to 3 carbon atoms are substituted. Preferred are tetramethylammonium hydroxide and tetraethylammonium hydroxide.

The amount of the alkaline substance used is 0.1 to 40% (weight / weight) with respect to the solvent, preferably 0.5 to
20% (weight / weight), more preferably 1-10%
(Weight / weight). This is because if the amount of the alkaline substance is too small, the unirradiated portion is not sufficiently dissolved, and if it is too large, there is a problem that it is not dissolved in the solvent or even the irradiated portion is dissolved.

When developing by immersing in the above-mentioned developing solution, the substrate on which the coating film is formed is simply immersed in the developing solution,
Alternatively, it is carried out by stirring the developing solution at the same time with the immersion, applying vibration, or applying ultrasonic waves. Alternatively, the coating film may be developed by spraying a developing solution. In this development operation, the temperature and time can be set so that the difference in dissolution between the exposed portion and the non-exposed portion is maximized, but in consideration of the ease of operation, the temperature is usually around room temperature (preferably 10). It is preferable to carry out at -60 ° C, particularly preferably 15-40 ° C for several seconds to several tens of minutes (preferably 30 seconds to 15 minutes). Then, after the above-mentioned development, the substrate on which the formed photo-cured film (relief pattern) has been formed is rinsed with an organic solvent that does not dissolve the photosensitive resin or water, and then a hot air drier and a hot plate. For example, it is preferable to perform heat treatment (post-baking) at a temperature of about 250 ° C. or lower, particularly 230 ° C. or lower for 1 to 60 minutes, especially 2 to 30 minutes.

[0034]

【Example】

Example 1 Production of Photosensitive Polyamide by Polycondensation of 3,5-Diaminobenzoic Acid Ethyl Methacrylate and Trimellitic Anhydride Chloride A three-necked flask was purged with dry nitrogen to replace the inside of the flask with 3,5-diamino. 19.85 g (0.75 mmol) of ethyl benzoic acid methacrylic acid ester was added, and to this, 120 ml of N-methyl-2-pyrrolidone (NMP).
Was added and dissolved. After dissolution, 15.82 g (0.75 mmol) of trimellitic anhydride chloride was added with stirring at 0 ° C., stirring was continued for 0.5 hours, and then the reaction was allowed to proceed at room temperature for 18 hours. After the reaction, the reaction solution containing 50 ml of NMP was added to a mixed solution of 1 liter of methanol and 1 liter of water to precipitate a polyamide. The precipitate was filtered off and dried to obtain 30 g of white polyamide powder.

[Example 2] 10 g of the polyamide powder obtained in Example 1, 0.1 g of methyl ether hydroquinone and 0.05 g of phenothiazine as a thermal polymerization inhibitor, 0.3 g of diethylthioxanthone as a photopolymerization initiator, and dimethylaminobenzoic acid. 0.4 g of acid ethyl ester and 0.3 g of benzyl, and 8 g of γ-glycidoxypropyltrimethoxysilane as an adhesion improver were dissolved in a mixed solution of 40 g of NMP and 10 g of diethylene glycol dimethyl ether, and then filtered through a 1 μm filter to obtain photosensitivity. A polyamide solution was obtained. The obtained solution was spin-coated on a glass substrate at 2000 rpm for 30 seconds using a spinner, and then this polyamide film was dried at 80 ° C. for 10 minutes to obtain a polyamide film having a thickness of 1.5 μm. At this time, two of the three carboxyl groups of the trimellitic acid unit in the polyamide were involved in the amide bond, and the remaining one was mostly present as [-COOH].

The polyamide film was passed through a test mask (Toppan Test Chart P, manufactured by Toppan Printing Co., Ltd.) 25
600 mJ using 0 W high pressure mercury lamp light (using Mikasa Co., Ltd., mask alignment device MA-10 type)
It was exposed so that the density would be / cm ² .

After the exposure, while stirring an aqueous solution containing 2.5% by weight of tetramethylammonium hydroxide ((CH ₃ ) ₄ NOH) and 5% by weight of ethyl cellosolve, a glass substrate having a polyamide film was added to the aqueous solution. It was immersed for 4 minutes, developed at room temperature, and washed with pure water. .
As a result, the polyamide film remained only in the exposed area. The pattern was then heated at 200 ° C for 30 minutes. The exposed polyamide film had a thickness of 1.3 μm. Further, this coating film was treated at 270 ° C., but no abnormality was found in the coating film. Further, when the transmittance of the coating film having a thickness of 1.5 μm was measured, the transmittance was 90% or more in 400 nm to 700 nm, and it was shown that the transparency was extremely good in the entire visible light wavelength region.

[Example 3] {Preparation of organic pigment-dispersed polyamide solution} To 86.0 g of triethylene glycol dimethyl ether, 3.5 g of anthraquinone red (Chromogai Red A2B, manufactured by Ciba-Geigy) was added, and after mixing and stirring, Ultrasonic waves of 50 W were applied for about 1 hour in a water tank to disperse the above pigment, and this solution was pressure-filtered using a 1 μm fluororesin filter (Teflon filter) to obtain a pigment dispersion. Then, to the above-mentioned pigment dispersion solution, hydroquinone monomethyl ether 0.2 was added as a thermal polymerization inhibitor.
6 g and the polyamide powder obtained in Example 1 above 8.
After adding 5 g and stirring thoroughly to make a uniform viscous liquid,
Ultrasonic waves of 30 W were applied for about 30 minutes in the water tank. 0.34 g of 4,4'-diazidochalcone was added to the viscous liquid thus obtained, and the mixture was stirred and filtered under pressure using a 1 μm fluororesin filter (Teflon filter) to give a red pigment. A polyamide solution (photosensitive composition) in which was dispersed was obtained.

[Formation of Colored Pattern] The above-mentioned photosensitive composition containing a red pigment was dried on a glass substrate to give a dry film thickness of 1.5.
The coating film was spin coated using a spinner to a thickness of μm, and the coating film was dried at 80 ° C. for 10 minutes to form a coating film (dry film) of the composition on the glass substrate surface. 1 on this coating surface
A stripe-shaped mask having an interval of 0 μm was brought into close contact with the mask, and exposed through the mask using an ultrahigh pressure mercury lamp (5 mW / cm ² ) so that the exposure amount was 600 mJ / cm ² . Then, the pattern-exposed coating film was developed with the same solution as in Example 2 for 4 minutes and heat-treated at 200 ° C. for 30 minutes to obtain a clear red pattern of 10 μm stripes.
The red pattern thus obtained was heated at 250 ° C. for 1 hour, but no discoloration or discoloration was observed.

Example 4 Green color was obtained in the same manner as in Example 3 except that N-methyl-2-pyrrolidone was used as the organic solvent and phthalocyanine green which was a green pigment was used in place of anthraquinone red which was a red pigment. A polyamide solution (photosensitive composition) in which the pigment was dispersed was obtained. Using the above-mentioned green pigment-containing photosensitive composition, a coating film (dry film) of the composition was formed on a glass substrate in the same manner as in Example 3, exposed, and developed to form a 10 μm stripe. A clear green pattern was obtained. The green pattern thus obtained was heated for 1 hour at 250 ° C.
No fading was observed.

[Example 5] Blue was obtained in the same manner as in Example 3 except that N-methyl-2-pyrrolidone was used as an organic solvent and phthalocyanine blue which was a blue pigment was used instead of anthraquinone red which was a red pigment. A polyamide solution (photosensitive composition) in which the pigment was dispersed was obtained. Using the blue pigment-containing photosensitive composition described above, a coating film (dry film) of the composition was formed on a glass substrate in the same manner as in Example 3, exposed, and developed to form a 10 μm stripe. A clear blue pattern was obtained. The blue pattern thus obtained was heated at 250 ° C. for 1 hour, but no discoloration or discoloration was observed.

[Example 6] The same as Example 3 except that 0.51 g of 2,6-di (4'-azidobenzal) -4-methylcyclohexanone was used in place of 4,4'-diazidochalcone. To obtain a polyamide solution (photosensitive composition) in which the red pigment was dispersed. Using the above-mentioned red pigment-containing photosensitive composition, a coating film (dry film) of the composition was formed on a glass substrate in the same manner as in Example 3, exposed, and developed to form a 10 μm stripe. A clear red pattern was obtained.
The red pattern thus obtained was heated at 250 ° C. for 1 hour, but no discoloration or discoloration was observed.

[0043]

EFFECTS OF THE INVENTION According to the present invention, a colored or uncolored pattern of a polyamide film excellent in heat resistance, insulation and colorless transparency is obtained by developing a solution of a photosensitive polyamide in a substantially aqueous solution. A method of forming can be provided.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI H01L 21/312 H01L 21/30 502R (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F 7/00-7 / 42

Claims (2)

(57) [Claims] 1. A aromatic diamine compound _{H 2 N-R 1 -NH 2} (I) ( provided that wherein R ₁ having a photosensitive group represented by the following following general formula (I) contains a photosensitive group The residue of the aromatic group is shown) 100 to 10 mol% and the following general formula (II).
Aromatic diamine compound H ₂ N—R ₂ —NH ₂ (II) containing no photosensitive group represented by the formula (wherein R ₂ represents a residue of an aromatic group containing no photosensitive group) 0 to A photosensitive polyamide comprising a copolycondensate of 90 mol% of an aromatic amine component, 100 to 10 mol% of an aromatic tricarboxylic acid compound and 0 to 90 mol% of an aromatic dicarboxylic acid compound. The solution is used to form a polyamide film, and the polyamide film is exposed in a predetermined pattern and then developed with an aqueous solution containing a basic compound to give a thickness not containing a coloring material.
400-700 measured on a 1.5 μm exposed coating
having a transparency of not less than 90% in nm.
A pattern characterized by forming a pattern of an amide film
Forming method. 2. The method for forming a pattern according to claim 1, wherein the solution of the photosensitive polyamide further contains a coloring material to form a colored pattern.