JP3365108B2 - 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 containing a photosensitive group and an acidic group in a polymer chain, which has excellent solubility in an aqueous alkaline solution, and more specifically, heat resistance, electrical properties and mechanical properties. The present invention relates to a photosensitive polyamide soluble in an alkaline aqueous solution, which is excellent in physical properties 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 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 compounding of a polyamide containing no photosensitive group and a photopolymerizable unsaturated compound (monomer), and thus the photosensitivity is not sufficiently high. (JP-A-48-
89004, JP-A-49-74739 and JP-A-56-
93794 etc.). Polyamides containing photosensitive groups have also been proposed (JP-A-50-8605 and JP-A-56).
-122833 etc.) 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 and transparency.

[0006]

SUMMARY OF THE INVENTION The present invention is an aromatic diamine compound having a photosensitive group represented by the following following general formula _{(I) H 2 N-R} 1 -NH 2 (I) ( In the formula R ₁ represents a residue of an aromatic group containing a photosensitive group.) 10 to 90 mol%, an aromatic diamine compound H ₂ N—R ₂ —NH containing an acidic group represented by the following general formula (II) ₂ (II) (wherein R ₂ represents a residue of an aromatic group containing an acidic group) 10 to 90 mol%, and a photosensitive group and an acidic group represented by the following general formula (III): Aromatic diamine compound H ₂ N—R ₃ —NH ₂ (III) not containing (wherein R ₃ represents a residue of a fragrance group containing no photosensitive group or acidic group) from 0 to 80 mol% Aromatic amine component, aromatic dicarboxylic acid compound, and aromatic dicara having an acidic group in addition to two carboxyl groups Bon acid compound, or solution to form a polyamide film with a photosensitive polyamide consisting co polycondensates of Na Ru Kaoru aromatic carboxylic acid component from one of the mixtures thereof, the polyamide film, a predetermined pattern -After exposing to light, the use of alkaline substances
The present invention relates to a pattern forming method, which comprises developing with an alkaline aqueous solution having a dose of 0.5 to 20% by weight with respect to a solvent .

[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 aromatic amine component is 10 to 90 mol% of the aromatic diamine compound having a photosensitive group represented by the general formula (I), and the aromatic diamine compound containing an acidic group represented by the general formula (II). 10 to 90 mol% and the general formula (II
It is composed of 0 to 80 mol% of an aromatic diamine compound represented by I) which does not contain a photosensitive group and an acidic group. General formula (I)
The component imparts photosensitivity to the polyamide, and the component of the general formula (II) is essential because it imparts alkali water solubility to the polyamide. Further, the general formula (III) 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 (I) component is 30 to 70%,
Component (I) is 30 to 70% and component (II) is 0 to 4
It is 0 mol%. When the amount of the general formula (III) component is too large,
This is because the concentration of the photosensitive group in the copolymer is lowered and the photosensitivity is lowered, 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 [carboxyethylmethacrylate ester is CH2 = C (CH3) COO
CH2 CH2 OOC-], 4-methyl-2'-carboxyethyl acrylate-3,4'-diaminodiphenyl ether [carboxyethyl acrylate is CH2 = CHCOOCH2 CH2 OOC-], 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.

Examples of the acidic group contained in the diamine compound represented by the general formula (II) include a hydroxyl group, a carboxyl group, a sulfonic acid group and alkali metal salts of these acidic groups. Of these, a hydroxyl group and a carboxyl group are preferable. The aromatic diamine compound in which the acidic group is a hydroxyl group may be a compound in which a hydroxyl group is directly bonded to an aromatic ring, and for example, as a compound having one hydroxyl group,
Examples of compounds having two hydroxyl groups such as 3,5-diaminophenol include, for example, 2,2-bis (3-amino-).
4-hydroxyphenylpropane, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-
Amino-4-hydroxyphenyl) sulfone, 3,3 '
-Diamino-4,4'-dihydroxybenzophenone,
Bis (3-amino-4-hydroxyphenyl) methane,
Bis (3-amino-4-hydroxyphenyl) ether, 1-phenyl-1,1-bis (3-amino-4-hydroxyphenyl) ethane, bis (3-amino-4-hydroxyphenyl) sulfide, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1-phenyl-1,1-bis (3-amino-4-hydroxyphenyl) trifluoroethane, 1-trifluoromethyl- 1,1-bis (3-amino-4-hydroxyphenyl) ethane, 1,1,3-trimethyl-3
(3'-Amino-4'-hydroxy) -5-hydroxy-6-aminoindan, 1,4-diamino-2,5-dihydroxybenzene, 1,5-diamino-2,4-dihydroxybenzene, 3,3 Examples thereof include'-diamino-4,4'-dihydroxyterphenyl.

The aromatic diamine compound in which the acidic group is a carboxyl group may be any compound in which a carboxyl group is directly bonded to an aromatic ring. For example, one having one carboxyl group is 3,5- Examples thereof include diaminobenzoic acid and 2,5-diaminobenzoic acid,
Examples of those having two carboxyl groups include 2,5-diaminoterephthalic acid and methylenebisanthranilic acid.

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

The above general formula (I) and the above general formula (I
The aromatic diamine compound represented by I) may be used in combination of two or more, if necessary, and the aromatic diamine compound represented by the general formula (III) used in combination therewith is also required. Accordingly, it is possible to use two or more kinds in combination.

The aromatic carboxylic acid component used in the present invention is an aromatic carboxylic acid compound having at least two carboxyl groups, and an aromatic dicarboxylic acid compound and an aromatic group having an acidic group in addition to the two carboxyl groups. Carboxylic acid compounds are preferred. Further, two or more kinds of these aromatic carboxylic acid compounds may be mixed and used.

Specific examples of the above aromatic dicarboxylic acid compound include terephthalic acid, isophthalic acid and 4,4 '.
There may be mentioned aromatic dicarboxylic acids such as -dicarboxy-biphenyl, 4,4'-dicarboxy-diphenylmethane, 4,4'-dicarboxy-diphenyl ether and their acid halides. Among these aromatic dicarboxylic acid compounds, acid halides of the above aromatic dicarboxylic acids, particularly acid chlorides, are preferable.

Examples of the aromatic carboxylic acid compound having an acidic group in addition to the above two carboxyl groups include aromatic tricarboxylic acid compounds, aromatic tetracarboxylic acid compounds and other aromatic compounds having three or more carboxyl groups, And aromatic dicarboxylic acid compounds having an acidic group other than a carboxyl group such as a sulfonic acid group and a hydroxyl group.

Examples of the above-mentioned aromatic tricarboxylic acid compounds include aromatic tricarboxylic acids, their anhydrides and their acid halides. Specifically, trimellitic acid or its anhydride, 3,3 ', 4- Tricarboxy-biphenyl or its anhydride, trimellitic anhydride chloride,

[0019]

[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.

As the above-mentioned aromatic tetracarboxylic acid,
Specifically, pyromellitic acid or its dianhydride, 3,
3 ', 4,4'-biphenyltetracarboxylic acid or its dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid or its dianhydride, 2,3,3 ', 4'
-Biphenyltetracarboxylic acid, or a dianhydride thereof,
2,3,3 ′, 4′-benzophenone tetracarboxylic acid, or a dianhydride thereof, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, or a dianhydride thereof may be mentioned. The compound may be an ester compound or a salt, but biphenyltetracarboxylic dianhydride is particularly preferable.

Specific examples of the aromatic dicarboxylic acid compound having an acidic group other than the carboxyl group such as the sulfonic acid group and the hydroxyl group include sulfone such as sodium- and potassium-3,5-dicarboxybenzene sulfonate. Aromatic dicarboxylic acid having an acid group, and 3
Mention may be made of hydroxyl-containing aromatic dicarboxylic acids, such as hydroxyphthalic acid, and their acid halides. Among these aromatic dicarboxylic acid compounds, acid halides of the above aromatic dicarboxylic acids,
Particularly preferred is an acid chloride.

The photosensitive polyamide used in the present invention is 0.5 g of polyamide / 100 m of N-methyl-2-pyrrolidone.
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 ratio of the aromatic carboxylic acid component and the aromatic diamine component used 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. The photosensitive polyamide obtained above is dissolved in an organic solvent, and a photopolymerization initiator and other additives are added to obtain a photosensitive composition. 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 derivative, 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.

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 compounded 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.

In the case of 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 obtain 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 may be prepared by a dispersion method such as a ball mill method, a roll method, an ultrasonic method or the like. 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-mentioned 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 dipped in the developing solution,
It is performed by stirring the developing solution, giving vibration, or applying ultrasonic waves. 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. And the like, at a temperature of about 250 ° C. or lower, particularly 230 ° C. or lower, 1 to
Heat treatment (post bake) for 60 minutes, especially 2 to 30 minutes
Preferably.

[0040]

【Example】

Example 1 Production of Photosensitive Polyamide by Polycondensation of 3,5-Diaminobenzoic Acid Ethyl Methacrylate and 3,5-Diaminobenzoic Acid with Terephthalic Acid Dichloride After replacing the inside of a three-necked flask with dry nitrogen. , 3,5-Diaminobenzoic acid ethyl methacrylic acid ester 13.14 g (0.497 mmol) and 3,5-diaminobenzoic acid 7.57 g (0.497 mmol) were added thereto, and N-methyl-2- Pyrrolidone (NMP) 130 ml was added and dissolved. After dissolution, stirring at 0 ° C., terephthalic acid dichloride 18.17 g
(0.895 mmol) was added, and stirring was continued at 0 to 10 ° C. for 2 hours to carry out a reaction. After the reaction, NMP5
The reaction solution containing 0 ml was added to a mixed solution of 1 l of methanol and 1 l of water to precipitate a polyamide. The precipitate is filtered off,
After drying, 30 g of white polyamide powder was obtained.

[Example 2] 10 g of the polyamide powder obtained in Example 1, 0.1 g of methyl ether hydroquinone as a thermal polymerization inhibitor and 0.05 g of phenothiazine, 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.

25 to this polyamide film through a test mask (Toppan Test Chart P manufactured by Toppan Printing Co., Ltd.)
600 mJ using 0 W high pressure mercury lamp light (using Mikasa Co., Ltd., mask alignment device MA-10 type)
Exposure was carried out to be / cm @ 2.

After the exposure, the glass substrate with the polyamide film was immersed in an aqueous solution containing 2.5% by weight of tetramethylammonium hydroxide ((CH3) 4NOH) and 5% by weight of ethyl cellosolve for 4 minutes for development. , Washed with more pure water. . As a result, the polyamide film remained only in the exposed area. Then, this pattern is subjected to 30 ° C. at 200 ° C.
Heated for minutes. The exposed polyamide film had a thickness of 1.0 μm. Further, this coating film was treated at 270 ° C., but no abnormality was found in the coating film.

Example 3 {Preparation of organic pigment-dispersed polyamide solution} 3.5 g of anthraquinone red (Chromogai Red A2B, manufactured by Ciba Geigy) was added as a red pigment to 86.0 g of triethylene glycol dimethyl ether, 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 N-methyl-as an organic solvent
A polyamide solution (photosensitive composition) in which a green pigment was dispersed was obtained in the same manner as in Example 3 except that 2-pyrrolidone was used and phthalocyanine green that was a green pigment was used instead of anthraquinone red that was a red pigment. It was 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 at 250 ° C. for 1 hour, but no discoloration or discoloration was observed.

Example 5 N-methyl-as an organic solvent
A polyamide solution (photosensitive composition) in which a blue pigment was dispersed was obtained in the same manner as in Example 3 except that 2-pyrrolidone was used and phthalocyanine blue which was a blue pigment was used instead of anthraquinone red which was a red pigment. It was 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 red 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,
A clear red pattern with 10 μm stripes was obtained. The red pattern thus obtained was heated at 250 ° C. for 1 hour, but no discoloration or discoloration was observed.

[0049]

According to the present invention, a method of forming a colored or non-colored pattern of a polyamide film having excellent heat resistance and insulation by developing a solution of a photosensitive polyamide in a substantially aqueous solution. Can be provided.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI H01L 21/027 H01L 21/312 B 21/312 21/30 502R 569E (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) is an aromatic containing photosensitive groups Aromatic diamine compound H ₂ N—R ₂ —NH ₂ (II) containing 10 to 90 mol% and an acidic group represented by the following general formula (II) Wherein R ₂ represents a residue of an aromatic group-containing aromatic group.) 10 to 90 mol%, and an aromatic diamine compound H ₂ containing no photosensitive group or acidic group represented by the following general formula (III) N—R ₃ —NH ₂ (III) (wherein R ₃ represents a residue of an aromatic group containing no photosensitive group or acidic group), an aromatic amine component consisting of 0 to 80 mol%, and an aromatic Group dicarboxylic acid compounds, aromatic dicarboxylic acid compounds having an acidic group in addition to the two carboxyl groups, or The polyamide film is formed by using a solution of a photosensitive polyamide consisting copolycondensates of either ing from Kaoru aromatic carboxylic acid component of the mixture, the polyamide film, a predetermined pattern - after exposure to emissions shape , The use of alkaline substances
A method for pattern formation, which comprises developing with an aqueous alkaline solution having a dose of 0.5 to 20% by weight based on the solvent . 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.