JPH0572941B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a photosensitive composition comprising a polyamide compound produced by a novel synthetic method and a photoactive substance selected from a photoinitiator, an azide compound, and a diazo compound. . More specifically, the present invention provides compositions useful as electrical and electronic component materials such as insulating materials and molding materials, particularly electronic materials such as semiconductor surface coating materials, LSI interlayer insulating films, and heat-resistant substrate materials. [Prior Art] Many polyamides derived from aromatic dicarboxylic acids are known. for example,
DuPont's polyamide (Nomex) has excellent tensile strength, tear strength, flexibility, toughness,
Because of its heat resistance and flame retardancy, it is being used not only as a fiber material but also as a general-purpose insulating material. Its uses include insulation for electric motors and transformers,
It is used in a wide range of applications, including various molded products such as coil bobbins, and parts for televisions and other products in response to demands for flame retardancy. Regarding methods for synthesizing these polyamides, the Morgan group at DuPont in the United States carried out systematic research on interfacial polycondensation using acid chloride and low-temperature solution polycondensation, and in 1958 they developed a method that could be easily synthesized under room temperature or outside conditions. It is said that a method has been established to synthesize this.
This is Morgan's book, Condensation
Polymers by Interfacial and Solution
Methods, (Condensation Polymers
(Interscience, New York, 1965)
I am familiar with These methods are often used to synthesize custom polyamides, and are also used for Nomex and Kevlar.
It has been adopted as an industrial manufacturing method for polyamides such as, and continues to this day. On the other hand, in recent years, the application of polyimide to semiconductor devices has also progressed. For example, as outlined in Sato et al.'s July issue of Functional Materials, page 9 (1983), a semiconductor element is coated with a special polyamide to form a film, which is then heated to form a polyimide film. It is converted into a film and used as a heat-resistant insulating film or a surface protection film. Furthermore, technologies that provide microlithography properties to these materials are also attracting attention. For example, by Lubner et al.
A polyamide having a photosensitive group via an ester bond, that is, a photosensitive polyimide precursor, as disclosed in Japanese Patent No. 41422, is known. By using this, a patterned polyimide surface protection film and interlayer insulating film can be easily formed on a semiconductor element or the like using a general lithography process. This polyamide is also basically synthesized by the aforementioned Morgan et al. synthesis method. [Problems to be Solved by the Invention] However, the polyamide synthesized by the method of Morgan et al. contains chlorine ions, and compositions containing materials containing these chlorine ions are used as surface coating materials in the field of electronic materials, When used in applications such as interlayer insulating films and junction coat films that come into direct contact with elements or metal wiring, the chlorine ions cause corrosion of semiconductors and their metals, or adversely affect electrical properties, which poses a problem. These matters are also explained by Sato et al. in Functional Materials, May issue, 1984, p. 49. Furthermore, it is extremely difficult to purify these polymers or compositions containing them using conventional methods to reduce the chloride ion concentration to several ppm or less. [Means for Solving the Problem] Based on the above background, the present inventors proceeded with the development of a photosensitive composition containing polyamide that contains only a sufficiently low concentration of chloride ions. Generally, components other than polymers, such as a photoinitiator and a solvent, contained in a photosensitive composition are low molecular weight compounds, and chloride ions can be removed relatively easily. Therefore, in order to reduce the chloride ion content of the composition, the chloride ion content of the polymer may be reduced. Based on the above idea, the present inventors developed a method for synthesizing polyamide that does not contain any chlorine ions. As a result of examining various chlorine-free dehydration condensation agents, it was found that among these, the use of carbodiimides gave the best results, leading to the completion of the present invention. That is, the present invention discloses a photosensitive composition containing a polyamide compound made from aromatic dicarboxylic acids and diamines using carbodiimides as a condensing agent, and a photoactive substance. The method for synthesizing the polyamide used in the composition of the present invention will be explained below. As the polycondensation method for the polyamide used in the composition of the present invention, melt polycondensation method, interfacial polycondensation method, solution polycondensation method, etc. can be selected, but since the produced polyamide can be easily isolated, etc. Solution polycondensation methods are most preferred. Examples of specific preferred solvents used in this case include tetrahydrofuran, γ-butyrolactone,
Dioxane, acetonitrile, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoryltriamide, chlorobenzene, acetone, methylethylketone, methylisobutylketone, cyclohexanone, cyclopentanone, methylene chloride, chloroform,
1,2-dichloroethane, chlorocene, ethyl acetate, diethyl ether, dimethyl sulfoxide,
Examples include tetramethylurea and pyridine.
Among these, aprotic polar solvents are more preferred in view of the solubility of the polyamide produced and the difficulty in causing side reactions. Various carbodiimides can be used. Specific preferred examples include dicyclohexylcarbodiimide, diethylcarbodiimide, diisopropylcarbodiimide, ethylcyclohexylcarbodiimide, diphenylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-cyclohexyl-3-(3-dimethyl aminopropyl) carbodiimide hydrochloride, carbodiimide, etc. Various dicarboxylic acids can be used depending on the intended use of the composition, but aromatic dicarboxylic acids are used because of the high heat resistance of polyamide or polyimide derived therefrom. Specific preferred examples include isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, methylterephthalic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4 '-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 1,1,
Examples include 1,3,3,3,-hexafluoro-2,2'-bis(4-carboxyphenyl)propane. In addition, as dicarboxylic acids, the following general formula

[Formula] (X is a 2+m-valent aromatic ring group or a heterocyclic group,
Y is -OR or

[Formula], R and R' are groups not containing a carboxyl group or an amino group, m is 1 or 2, and COY and COOH are in an ortho-position or a peri-position relationship with each other. ) When polyamide is used, it can be heated and cyclized to form an imide ring in a later step, resulting in a polyamide-imide or polyimide precursor having extremely high heat resistance. A specific preferred example thereof is trimellitic acid-2-
Ethyl ester, trimellitic acid-1-diethylamide, pyromellitic acid-2,5-dimethyl ester, mixture of pyromellitic acid-2,4-diethyl ester and pyromellitic acid-2,5-diethyl ester, naphthalene-1,4,5, 8-tetracarboxylic acid-1,5-diethyl ester, naphthalene-
2,3,6,7-tetracarboxylic acid-2,6-bisdimethylamide, 3,3',4,4'-diphenyltetracarboxylic acid-3,4'-diisopropyl ester, 1,1,1, 3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane diethyl ester, benzophenone-3,3',4,4'-tetracarboxylic acid diethyl ester, bis(3, 4-dicarboxyphenyl)
Ether dimethyl ester, bis(3,4-dicarboxyphenyl)sulfone diphenyl ester, ethylenetetracarboxylic acid diethyl ester, 2,3-dicarboethoxy-1,4-butanedicarboxylic acid, 3,4-dicarboxylic acid Examples include methoxyadipic acid and 3-carboxyglutaric acid-1-ethyl ester. In addition, by using a dicarboxylic acid having a photosensitive group such as a carbon-carbon double bond in the polyamide contained in the composition of the present invention, it is possible to absorb visible light without adding a separate compound having a photosensitive group.
It can be cured with ultraviolet rays, X-rays, electron beams, etc., and patterns can be drawn using photolithography. Specific preferred examples include 4-carboxycinnamic acid, p-phenylene diacrylic acid, allyl trimellitate, trimellitate (2-acryloxyethyl), 4,4'-dicarboxychalcone, di(4 -carboxybenzylidene)
Mention may be made of acetonic acid. In addition, when the above-mentioned photosensitive group is substituted at the ortho-position or peri-position of the carboxylic acid through a carboxylic acid ester bond, it becomes a photosensitive polyimide precursor, which has the best properties such as processability, heat resistance, and voltage resistance. It will be good. Specific preferred examples include 1,4-diallyl pyromellitate, 1,4-di(2-acryloxyethyl) pyromellitate,
Mixture of 1,4-di(2-methacryloxyethyl) pyromellitate and 2,4-di(2-methacryloxyethyl) pyromellitate, benzophenone-
3,3′,4,4′-diallyl tetracarboxylate,
3,3',4,4'-benzophenonetetracarboxylic acid-3,3' or 4,4' or 3,4'-di(2-
methacryloxyethyl) mixture, etc. These dicarboxylic acids can be used alone or in combination of two or more. Various diamines can be used depending on the intended use of the composition. For example, aliphatic or alicyclic diamines can be used, and specific preferred examples thereof include ethylene diamine, 1,3-propylene diamine, 1,2
-Propylenediamine, 1,4-butanediamine, 2,2-dimethyl-1,3-propylenediamine, hexamethylenediamine, 1,4-cyclohexanediamine, 3-methoxyhexamethylenediamine, decamethylenediamine, bis(3- Examples include aminopropyl) sulfide, bis(4-aminocyclohexyl)methane, piperazine, and the like. In addition, polyamides with high heat resistance can be produced by using aromatic diamines, and specific preferred examples thereof include meta-phenylene diamine, para-phenylene diamine, 4,4'-diaminodiphenylpropane, 4, 4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfon,
4,4'-diaminodiphenyl sulfide, benzidine, 4,4'-diaminodiphenyl ether,
1,5-diaminonaphthalene, meta-toluidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,4'-diaminodiphenyl ether, 3,3'-dimethoxybenzidine, ortho- Toluidine sulfon, phenylindane diamine, 1,1,1,3,3,3,-hexafluoro-2,2-bis(4-aminophenyl)propane, 1,1,1,3,3,3,- Hexafluoro-2,2-bis(4-aminophenoxyphenyl)propane, bis(4-aminophenoxyphenyl)sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,9-bis(4 -aminophenyl)fluorene, 4,4'-diaminobenzanilide, bis(4-β-amino-t-butylphenyl)ether, metaxylylene diamine, and the like. Furthermore, in order to improve adhesiveness, a diamine having a siloxane structure can be copolymerized within a range that does not reduce heat resistance. Preferred examples include those represented by the following structural formula.

【formula】

[Chemical formula] These diamines may be used alone or in combination of two or more. The reaction conditions for producing the polyamide used in the composition of the present invention are not particularly limited, and known conditions can be employed. The reaction temperature is not particularly limited as long as the reaction proceeds, but from the viewpoint of reaction rate and generation of by-products, -20°C to 80°C is preferable, and -10°C
to 30°C is more preferable. The ratio of the condensing agent may be at least equivalent to the amount of the carboxylic acid or amine, whichever is smaller, and there is no particular problem even if the amount is present in excess. It is usually preferable to use about 1 equivalent to 1.5 equivalents. The amount of solvent is 500% per mole of condensing agent.
Preferably from ml to 10. The reaction time is
Preferably 10 minutes to 100 hours, 1 hour to 24 hours
Time is even more preferred. It is also preferable to use additives such as 1-hydroxybenzotriazole, N-hydroxysuccinimide, and pyridine during the reaction to facilitate the reaction. Although the reagents can be added in any order, it is better to add the solvent and dicarboxylic acids first, then add the carbodiimides, and then add the diamines. It is preferable because it can synthesize. The molar ratio of dicarboxylic acids and diamines is preferably around 1.0, but can also be set to 0.7 to 1.3 depending on the molecular weight of the target polyamide.
Furthermore, the molecular weight can also be controlled by adding monofunctional alcohols, amines, etc. during the reaction. To stop the reaction, known methods such as diluting the reaction solution, isolating the produced polyamide, and inactivating active reaction terminals with alcohol or the like can be used. Isolation of the polyamide used in the composition of the invention includes:
Depending on the properties of the produced polyamide and the properties of the condensing agent used, the solvent,
This can be carried out by removing the remaining condensing agent, ureas that are products from the condensing agent, and the like. The photoactive substance of the present invention is selected among photoinitiators, azide compounds, and diazo compounds. Various azide compounds can be selected for use in the composition of the present invention. Specific preferred examples include 1,4-benzenebisulfonazide, 4-sulfonazidophenylmaleimide, 4,4'-diazidochalcone, 1,3-bis(4-azidobenzaru)acetone, 2,6-bis(4-azidobenzalu)cyclohexane,
Examples include 2,6-bis(4-azidobenzalu)4-methylcyclohexane. Various diazo compounds can be selected for use in the composition of the present invention. As a specific preferable example, 4-diazo-N-ethyl-N-β
-hydroxyethylaniline, 1,2-naphthoquinonediazide-4-sulfonic acid, p-benzoquinonediazide-p-diazophenylamine, and the like. A variety of photoinitiators can be selected for use in the compositions of the present invention. Specific preferred examples thereof include benzophenone, methyl o-benzoylbenzoate, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4,4'-dichlorobenzophenone. ,
4-benzoyl-4'-methyldiphenylketone,
Benzophenone derivatives such as dibenzyl ketone and fluorenone. 2,2'-diethoxyacetophenone,
2-hydroxy-2-methylpropiophenone,
Acetophenone derivatives such as p-s-butyldichloroacetophenone. 1-Hydroxycyclohexyl phenyl ketone. Thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-
Thioxanthone derivatives such as isopropylthioxanthone and diethylthioxanthone. Benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal and other benzyl derivatives. Benzoin derivatives such as benzoin, benzoin methyl ether, and benzoin isobutyl ether. Anthraquinone derivatives such as anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, and β-chloroanthraquinone. Anthrone derivatives such as anthrone, benzanthrone, dibenzosuberone, methylene anthrone, etc. 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)
Oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyloxime), oximes such as α-benzoin oxime, naphthalenesulfonyl chloride, quinolinesulfonyl chloride,
N-phenylthioacridone, 4,4'-azobisisobutyronitrile, diphenyl disulfide,
Reduction of photoreducible dyes such as benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenyl sulfone, benzoyl peroxide, and eosin, methylene blue, ascorbic acid, triethanolamine, etc. combination of agents, etc. A suitable sensitizer can also be added to the photoinitiator. Examples of sensitizers include triethylamine, diethanolaniline, Michler's ketone, isoamyl dimethylaminobenzoate, ethyl diethylaminobenzoate, and sensitizing dyes. These photoactive substances can be used alone or in mixtures of several types. These initiators are added to the photosensitive composition in an amount of 0.1 to 20% based on the polyamide. A compound having a carbon-carbon double bond can be added to the composition of the present invention, if necessary. This compound having a carbon-carbon double bond is a compound that facilitates the photopolymerization reaction when added, and examples of such compounds include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, N-vinyl -2-pyrrolidone,
carpitol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate,
1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate,
Dipentaerythritol hexaacrylate tetramethylolmethane tetraacrylate, the above acrylates changed to methacrylates, methylene bisacrylamide, N-methylol acrylamide, di(acrylaminomethyl) ether, the above acrylamides changed to methacrylamide, N -phenylmaleimide, diphenylmethane-4,4'-bismaleimide, trimethylolpropane triallyl ether, pentaerythritol triallyl ether, etc. Preferred among these are It is a compound with heavy bonds. These compounds having a carbon-carbon double bond can be added to the polyamide in an amount of 50% or less, if necessary. In addition, when an allyl ether compound is used as the above-mentioned compound having a carbon-carbon double bond, and when a polyamide is synthesized from a dicarboxylic acid having a sensitive group of a carbon-carbon double bond, the sensitive group is When using an allyl group, it is preferable to use it in combination with an azide compound as a photoactive substance, or as a composition containing a photoinitiator and a polythiol compound. These polythiol compounds have the general formula

[Chemical formula] (However, R ₁ and R ₂ are organic groups that do not contain a "reactive" unsaturated carbon-carbon bond group, and n is an integer of 2 or more.) Here, "reactive carbon-
The term "carbon unsaturated bond group" refers to a group that reacts with a thiol group under appropriate conditions to form a thioether bond.

[Effect]

In the composition of the present invention, after the coating film is formed, a crosslinking reaction is caused between molecules using actinic rays, and an image is obtained by utilizing the difference in dissolution rate between crosslinked and uncrosslinked parts in organic solvents, etc. It is. Furthermore, since the composition of the present invention has a low content of chlorine ions, corrosion of metals catalyzed by chlorine ions does not progress, and performance such as reliability when used as a protective film for various purposes is improved. Furthermore, when water is present in the system, chlorine ions promote the hydrolysis of polyamide and have a negative effect on the storage stability of polyamide solutions, but the composition of the present invention has a low content of chlorine ions, so it can be stored well. Has stability. [Effects of the Invention] The composition of the present invention does not use a chlorine-containing condensing agent in the synthesis of the raw material polyamide, so it does not contain chlorine ions exceeding the detection limit and does not cause problems such as metal corrosion, so it is widely used. It can be applied to electronic materials and semiconductor fields. Further, the solution of the composition of the present invention has practical advantages such as good storage stability and easy management during use. [Example] Examples of the present invention are shown below, but the present invention is not limited thereto. Synthesis Example 1 In a 300 ml separable flask, 16.6 g of isophthalic acid, 100 ml of N-methylpyrrolidone, 4.
20.0 g of 4'-diaminodiphenyl ether and 0.5 g of pyridine were added, and a solution of 41.2 g of dicyclohexylcarbodiimide in 40 ml of N-methylpyrrolidone was added dropwise over 30 minutes while stirring under ice cooling. After further stirring for 24 hours at room temperature, 5 ml of ethanol was added and the mixture was stirred for an additional 4 hours. The precipitate was filtered, and the resulting solution was added to 10 parts of ethanol under stirring. The resulting precipitate was filtered and washed with ethanol. , and vacuum dried to obtain a white powder (27.0 g). The obtained powder had a viscosity number (ηsp/C) of 0.50 dl/g at 30° C. and 0.5 g/dl in concentrated sulfuric acid. The weight average molecular weight determined by gel permeation chromatography (GPC) was 50,000. this
It is called PA-1. The above method is referred to as synthesis method A. Comparative Synthesis Example 1 In a 300 ml separable flask, 19.8 g of diaminodiphenyl ether and N-methylpyrrolidone were added.
100 ml and 17.0 g of pyridine were added, and 20.3 g of isophthalic acid dichloride was added dropwise over 15 minutes while stirring under ice cooling. After further stirring at room temperature for 24 hours, 5 ml of ethanol was added and the mixture was further stirred for 4 hours. The obtained solution was added dropwise to 100 g of water under stirring, and the resulting precipitate was filtered, washed with water and ethanol, and then dried under vacuum to obtain a white powder (26.0 g). The obtained powder had a viscosity number (ηsp/C) of 0.48 dl/g at 30°C and 0.5 g/dl in concentrated sulfuric acid. The weight average molecular weight determined by GPC was 47,000. this
It is called PA-2. Reference Example 1 100 g of pyromellitic anhydride was placed in a 300 ml flask, 200 ml of ethanol was added, and the mixture was heated to 70° C. for 1 hour. After cooling, the formed crystals were separated and recrystallized with ethanol to obtain pyromellitic acid-1,4-diethyl ester (44.0 g). The nuclear magnetic resonance spectrum of this compound showed the following absorption. δ value 1.40
Triple line, 6H equivalent; 4.40, Quadruple line, 4H equivalent; 8.03,
Single line, 2H equivalent; 11.50, wide, 2H equivalent. Synthesis Example 2 Put 31.0 g of pyromellitic acid-1,4-diethyl ester, 1.00 ml of γ-butyrolactone, and 17.0 g of pyridine into a 500 ml separable flask, and add dicyclohexylcarbodiimide while stirring under ice cooling.
A solution of 41.2 g of γ-butyrolactone in 40 ml was added dropwise over 10 minutes. Furthermore, under ice cooling, a solution of 20.0 g of 4,4'-diaminodiphenylmethane and 100 ml of γ-butyrolactone was added dropwise over 15 minutes. After further stirring at 10°C for 8 hours, 5 ml of ethanol was added, and the mixture was further stirred at room temperature for 4 hours to remove the precipitate.
The resulting precipitate was filtered, washed, and dried under vacuum to obtain a pale red powder (42.0 g). The viscosity number (ηsp/
C) was 0.30 dl/g. The weight average molecular weight determined by GPC was 27,000. This is PI-/
It is called. The above method is referred to as synthesis method B. Reference example 2 Allyl alcohol is placed in a four-necked flask equipped with a stirrer, a reflux condenser with a drying tube, and a thermometer.
Add 349g and 500g of 3,3'-4,4'-benzophenonetetracarboxylic dianhydride and heat at 100℃ in an oil bath.
I stirred it for 3 hours. After cooling, allyl alcohol was distilled off from the reaction mixture using an evaporator, and 674 g of solid was obtained by vacuum drying. This product is designated as C-1. The nuclear magnetic resonance spectrum (100 MHz, solvent C _D Cl ₃ ) of C-1 showed the following absorption. (δ value 4.8ppm, double line, 4H equivalent), (5.1~
5.6, multiplet, 4H), (5.7~6.2, multiplet, 2H),
(7.8-8.5, multiplet, 6H), (8.9, singlet, 2H). Synthesis Example 3 In a 200 ml separable flask, add C-1
22.2g, gamma butyrolactone 71.4ml, pyridine 9.1
ml and 8 g of 4,4'-diaminodiphenyl ether
was added and stirred at room temperature for 30 minutes to obtain a homogeneous solution. To this solution, 20.6 g of dicyclohexylcarbodiimide was added while cooling with ice/water, and after stirring for 3 hours, 5 ml of ethanol was added, and the mixture was further stirred for 1 hour. The reaction mixture was filtered and the solution was added dropwise to methanol under stirring, and the precipitate formed was separated by decantation. This precipitate,
It was dissolved in 186 ml of THF and added dropwise to 1.5 ion exchange water while stirring. Filter the formed precipitate,
After air drying, it was vacuum dried to obtain 22.0 g of red powder. N-
The viscosity number (ηsp/C) at 30° C. and 1 g/dl in methylpyrrolidone was 0.14. The weight average molecular weight determined by GPC was 16,000. This is PI-2
It is called. The above method is referred to as synthesis method C. Synthesis Example 4 21.8 g of pyromellitic anhydride, 27.0 g of 2-hydroxyethyl methacrylate, and 100 ml of γ-buketyrolactone were placed in a 500 ml separable flask, and 17.0 g of pyridine was added while stirring under ice cooling. After stirring at room temperature for 16 hours, add 41.2 g of dicyclohexylcarbodiimide to 40 ml of gamma butyrolactone.
was added over 10 minutes under ice-cooling, followed by addition of 4,4'-
16.0 g of diaminodiphenyl ether was added over 15 minutes. After stirring for 3 hours under ice cooling, ethanol 5
ml was added and stirred for an additional 1 hour to filter out the precipitate.The obtained solution was added to 10 parts of ethanol, and the resulting precipitate was washed with ethanol and vacuum dried to obtain a pale colored powder. N- of the obtained powder
The viscosity number (ηsp/C) at 30° C. and 1 g/dl in methylpyrrolidone was 0.22. The weight average molecular weight determined by GPC was 13,000. Typical absorption values for nuclear magnetic resonance spectra are δ values of 0.9 to 1.8.
(Wide); 1.8 (s, 6H equivalent); 4.5 (wide, d, 8H equivalent); 5.6 (s, 2H equivalent); 6.0 (s, 2H equivalent); 7.0
(d, equivalent to 4H); 7.7 (d, equivalent to 4H); 7.7 to 8.4 (m,
(equivalent to 2H). Here, s represents a singlet, d represents a doublet, and m represents an absorption of a multiplet.
50 of the end of the polymer from the integral value of absorption between 0.9 and 1.8
% was estimated to have an acylurea structure. Typical absorption value of infrared absorption spectrum in cm
^-1 indicates 1730, 1660, 1610, 1540, 1500,
They were 1450, 1410, 1300, 1240, 1165, 1100.
This is called PI-3. The above method is referred to as synthesis method D. Comparative Synthesis Example 2 Into a 500 ml separable flask, put 21.8 g of pyromellitic anhydride, 27.0 g of 2-hydroxyethyl methacrylate, and 100 ml of γ-butyrolactone.
While stirring under ice cooling, 33.0 g of pyridine was added. After stirring at room temperature for 16 hours, 23.8 g of thionyl chloride was added over 30 minutes at 10-15°C. 1 hour 15
After the mixture was left to stand at °C, a slurry of 16.0 g of 4,4'-diaminodiphenyl ether and 50 ml of γ-butyrolactone was added dropwise under ice cooling for 30 minutes. After being left at 15°C for 2 hours, 10 ml of ethanol was added and left at room temperature for 16 hours. The obtained solution was diluted to 2 times with γ-butyrolactone, and then added dropwise to 10 mL of ion-exchanged water with stirring. After filtering and washing the precipitate, it was dissolved again in 100 mL of tetrahydrofuran, and 10
into ion-exchanged water, filter the precipitate, wash it,
After drying, 50.0 g of pale yellow powder was obtained. The viscosity number (ηsp/C) of the obtained powder in N-methylpyrrolidone at 30°C and 1 g/dl was 0.19. The weight average molecular weight determined by GPC was 15,000. PI this
-4.

[Table] Reference Example 3 Measurement of chloride ion concentration The chloride ion concentration of all synthesized polymers was determined by dissolving the polymer in an organic solvent to which a small amount of sulfuric acid solution was added, and titrating with a silver nitrate aqueous solution while measuring the electrical conductivity. was measured. 60ppm for PA-2,
PI-4 contained 80 ppm of chloride ions, while the other polymers contained no chloride ions, which were below the measurement limit. Note that the measurement limit value of this measurement method is approximately 1 ppm. Example 1 PA-1 25g, ethylene glycol diacrylate 10g, Michler's ketone 0.1g, benzophenone 0.5g, benzyl dimethyl ketanol 1.0g
was dissolved in 50 g of N-methylpyrrolidone to obtain a homogeneous solution. This solution was applied to a copper-clad glass epoxy laminate whose surface had been smoothed by buffing, and
It was dried at ℃ for 3 hours to obtain a uniform coating film with a thickness of 40 μm. Next, exposure was performed for 5 minutes in a nitrogen atmosphere using a photomask and an ultra-high pressure mercury lamp (8 mW/cm ² ), and then spray development was performed for 30 seconds with an equal mixture of N,N-dimethylacetamide and ethanol. A polyamide pattern was obtained. When this is dried at 280℃ for 2 hours in a nitrogen atmosphere, it has sufficient surface hardness, and when dried at 260℃ in a soldering bath,
Even after immersion for 10 seconds, no change in appearance was observed in the pattern. Furthermore, this pattern was left in an environment with a temperature of 80°C and a humidity of 85% for 200 hours, but no change occurred in the appearance of the copper surface under the coating. Comparative Example 1 A pattern was formed using PA-2 under the same conditions as in Example 1 except for the following conditions. When the resulting pattern was left in an environment with a temperature of 80°C and a humidity of 85% for 200 hours, cloudiness appeared on the copper surface under the coating, which was thought to be due to corrosion. Examples 2 to 7 PA-3, PA-4, PA-5, PAI-1, PAI
-2, pattern formation was performed under the same conditions as in Example 1. After heat-treating each pattern at an appropriate temperature, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

[Table] Reference Example 4 The solutions of Examples 1, 2, and 4 and Comparative Example 1 were allowed to stand at room temperature, and changes in solution viscosity were observed. In the solution of Comparative Example 1, the solution viscosity decreased after 3 days, but
Others showed no change even after 7 days. Example 8 20 g of PA-4 and 0.8 g of 2,6-bis(4-azidobenzalu)cyclohexane were dissolved in 20 g of cyclohexanone to obtain a homogeneous solution. This was spin-coated onto a silicon wafer and dried at 60°C for 1 hour to obtain a coating film with a thickness of 10 μm. Next, the film was exposed to light for 10 seconds using a photomask and an ultra-high pressure mercury lamp (8 mW/cm ² ), and then developed using a mixed solvent system of cyclohexanone and xylene.
A pattern was obtained by drying at ℃ for 2 hours. The pattern had a resolution of 10 μm. Example 9 25 g of PI-2, 1.25 g of pentaerythritol tetra(3-mercaptopropionate), 0.5 g of Michler's ketone, 1.0 g of Countercure PDO manufactured by Ward-Plenkinsop, and 1-phenyl-5-mercapto-1H- 0.125g of tetrazole, 15ml of N-methylpyrrolidone and 15ml of cyclopentanone
ml of mixed solution to obtain a homogeneous solution. This solution was spin-coated on a silicon wafer pretreated with NUC Silicone A-187 at 1000 revolutions for 7 seconds, and dried at 70°C for 3 hours to form a film with a thickness of 50 μm.
A uniform coating film was obtained. Then, under a nitrogen atmosphere,
Using an ultra-high pressure mercury lamp with an output of 8mW/ ^cm2
Exposure to 480 mJ/ ^cm2 , then use a spray developing machine to develop with an equal mixture of γ-butyrolactone and xylene for 30 seconds, spray xylene for 10 seconds, rinse, and then apply nitrogen spray. After thorough drying, a patterned coating film was obtained only in the exposed areas. At this time, it was confirmed that the pattern resolved 60μ lines. Next, this coating film was heat-treated at 400℃ for 1 hour in a nitrogen atmosphere, resulting in a film thickness of 38μ.
A pattern of polyimide coating was obtained. Example 10 The same composition as in Example 9 was used, except that 3.75 g of trimethylolpropane trithioglycolate was used instead of pentaerythritol tetra(3-mercaptopropionate), and 44 ml of these were used.
of N-methylpyrrolidone to obtain a homogeneous solution. This solution was spin-coated for 20 seconds at a rotational speed of 2000 rpm, and the resulting coating film was dried at 70° C. for 30 minutes. The film thickness was measured with a contact film thickness meter (Talystep, manufactured by Taylor Bogson) and was found to be 4.8μ. Next, the film was exposed in the same manner as in Example 9, developed for 5 seconds with a mixed solution of equal amounts of γ-butyrolactone and xylene, rinsed with xylene for 10 seconds, and dried with nitrogen spray. Thereafter, the film thickness was measured for each step exposure amount. The value obtained by dividing this film thickness by the film thickness before exposure is defined as "TD". As a method of expressing sensitivity, the exposure amount that gives TD = 0.5 is
Defining Dg [50] and the exposure amount Dg [80] that results in TD = 0.8, in this example, Dg [50] = 50 mJ/cm ² , Dg
[80] = 70mJ/ ^cm2 . We also confirmed that it was able to resolve 5μ lines. TT was 0.75. Example 11 20 g of PI-3, 0.4 g of Michler's ketone, 0.4 g of 4-azidosulfonyl phenylmaleimide
was added to 22 g of N-methylpyrrolidone to obtain a homogeneous solution. A uniform coating film with a thickness of 70 μm was obtained from this solution in the same manner as in Example 9. By subjecting this coating film to the same treatment as in Example 9,
A polyimide coating pattern with a film thickness of 32μ and a resolution of 60μ was obtained. Example 12 The thermal decomposition onset temperature of the polyimide coating film obtained in Example 11 was measured using a differential thermal balance under a nitrogen atmosphere and found to be 440°C. In addition, when PI-4 was treated in the same manner as in Example 11 and the thermal decomposition onset temperature of this polyimide coating was measured in the same manner, it was found to be 430
It was warm at ℃. Example 13 20 g of PI-3, 1.0 g of trimethylolpropane triacrylate, 1.0 g of Kantacure PDO from Ward-Plenkinsov, and 0.5 g of Michler's ketone.
and 1-phenyl-5-mercapto-1H-tetrazole 0.2g, diphenylnitrosamine 0.02
g, and these were dissolved in a mixed solvent of 15 ml of N-methylpyrrolidone and 15 ml of cyclopentanone to obtain a homogeneous solution. Add this solution to adhesion aid A187
It was dropped onto a silicone wafer pretreated with (NUC Silicone), spin-coated for 20 seconds at a rotation speed of 2000 rpm, and the resulting coating film was dried at 70° C. for 1 hour. When the film thickness was measured with a dial gauge, it was 15μ. Next, under a nitrogen atmosphere, using an ultra-high pressure mercury lamp (8 mW/cm ² ) and a photomask,
Exposure was made for 30 seconds. Next, using a spray developing machine, develop with a mixture of equal amounts of γ-butyrolactone and xylene for 10 seconds, then spray xylene for 10 seconds to rinse, dry with nitrogen spray, and dry at 70°C. I did this. The pattern had sufficient surface hardness. Then this pattern
Heating was performed at 140°C for 2 hours and at 400°C for 2 hours to obtain a polyimide pattern. The resulting pattern is 10μm
It had a resolution of Reference Example 5 For PI-3, 4, and 5, a polyimide pattern was formed on the mirror surface of aluminum immediately after vapor deposition in the same manner as in Example 13. This is heated to 80℃ and humidity 90%.
When left for 1000 hours under these conditions, there was no change in PI-3 and 5, but clouding occurred on the aluminum mirror surface of PI-4. In addition, a silicon oxide film was formed on a silicon wafer, 300 aluminum wirings with a width of 3 μm and a thickness of 1 μm were formed on the film, and a polyimide film was formed using PI-3, 4, and 5 using the method described above. was formed. When a voltage of 20V was applied to this and it was left for 2000 hours at 80℃ and 90% humidity, there was no change in the products using PI-3 and 5.
The one using PI-4 had 14 wire breaks.

Claims (1)

[Claims] 1. A photosensitive composition comprising a polyamide compound made from an aromatic dicarboxylic acid and a diamine using a carbodiimide as a condensing agent, and a photoactive substance selected from a photoinitiator, an azide compound, and a diazo compound. .