JPH08146608A - Photosensitive resin composition and production of electronic device using the same - Google Patents

Abstract

PURPOSE: To obtain a polarity changing type photosensitive resin compsn. which is soluble with water and can be developed with a water-base solvent by incorporating a material which produces a base by irradiation of electromagnetic waves, a material which produces base by base, and a polymer compd. which changes its polarity by base. CONSTITUTION: This compsn. contains a material which produces base by irradiation of electromagnetic waves, a material which produces base by base, and a polymer compd. which changes its polarity by base. Namely, the compsn. contains a carboxylic acid polymer expressed by formula having 10000-1000000 mol.wt. by >20wt.% of the whole resin amt. and a secondary or/and tertiary amine by 0.01-1 equiv. to one equiv. of the carboxyl group in the carboxylic acid polymer. Further, the compsn. contains a photo-base producing agent which produces base by irradiation of electromagnetic waves by 0.01-0.5 equiv. to one equiv. of the carboxyl group, and a base-base producing agent which produces base by base by 0.1-2 equiv. to one equiv. of the carboxyl group. In formula, A is an org. group having >=2 carbon number, n is an integer, and R<1> is an org. group having >=1 carbon number.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photosensitive resin composition, a pattern forming method thereof and an electronic device manufacturing method using the same.

[0002]

2. Description of the Related Art Photosensitive resin compositions are widely used in the field of electronic devices such as large-scale integrated circuits as materials that can greatly simplify the wiring forming process. These photosensitive resin compositions have a positive type in which exposed areas are etched,
It is roughly classified into a negative type in which an unexposed portion is etched.

The negative-working photosensitive material is generally disadvantageous in forming a high-resolution fine pattern because the exposed portion (the portion which is not etched out) is swollen by the developing solution. Further, such an electronic device may require a positive photosensitive material in the process, and thus a positive photosensitive material has been desired. In particular, from the viewpoints of environmental pollution and work environment, there is a problem in using a conventional developer containing mainly a chlorine-based solvent or an organic solvent, and a photosensitive resin composition which can be developed with an aqueous solvent instead thereof is desired. .

In recent years, in the semiconductor industry, inorganic materials such as silicon oxide have been widely used as insulating films and passivation films for devices.

On the other hand, organic materials are excellent in low stress and smoothness as compared with inorganic materials, and high purity films can be formed. Therefore, in recent years, organic materials are used for insulating films and passivation films of semiconductor elements. Was developed and has already been put to practical use in some semiconductor devices.

However, since the semiconductor element undergoes working steps such as die bonding, the organic material is required to have thermal stability. Therefore, polyimides having excellent heat resistance have been widely studied.

For example, after coating a substrate with polyamic acid, which is a polyimide precursor, and performing heat treatment to convert it into polyimide, a photoresist relief pattern is formed on the polyimide film, and the polyimide film is formed with a hydrazine-based etching agent. The relief pattern is transferred to polyimide by selective etching.

[0008]

However, since the patterning of the polyimide includes steps such as photoresist coating and peeling, the working steps are complicated. In addition, the transfer of the relief pattern through the photoresist causes a decrease in dimensional accuracy. Therefore, a photosensitive heat-resistant material that can be finely processed by direct light has been desired.

As the above-mentioned photosensitive material, a photosensitive heat-resistant material comprising polyamic acid and dichromate (Japanese Patent Publication No.
17374), a photosensitive polyamic acid derived from a pyromellitic acid derivative (JP-A-49-112241), and a photosensitive heat-resistant material comprising a polyamic acid and an unsaturated amine compound (JP-A-54-145794). ), A photosensitive heat-resistant material obtained by reacting a polyamic acid and a saturated epoxy (JP-A-55-45746), and the like. However, since all of these photosensitive heat-resistant materials are negative type, swelling of the exposed portion occurs with the developing solution, which is a problem in performing high-resolution fine processing.

On the other hand, as the positive type photosensitive heat-resistant material,
Japanese Examined Patent Publication No. 1-59571, JP-A-62-229242
Japanese Patent Laid-Open No. 6-43648 and the like are proposed.
However, in these positive-type photosensitive heat-resistant materials, the amount of light irradiation for forming a pattern is relatively large, and the film thickness is limited because light is likely to be absorbed on the film surface due to coloring due to photochemical reaction. There is a problem to say.

An object of the present invention is to provide a water-soluble and polarity-changeable photosensitive resin composition which can be developed with an aqueous solvent, which solves the above problems.

Another object of the present invention is to provide a method of manufacturing an electronic device using the above photosensitive resin composition.

[0013]

The gist of the present invention for achieving the above object is as follows.

(1) A photosensitive resin composition comprising a substance that generates a base upon irradiation with electromagnetic waves, a substance that generates a base by the base, and a polymer compound whose polarity is changed by the base.

(2) Formula [1]

[0016]

[Chemical 11]

(Wherein A is an organic group having 2 or more carbon atoms, n is an integer, and R ¹ is an organic group having 1 or more carbon atoms, a hydrogen atom or a halogen atom). , 0
20 to 20% by weight of the carboxylic acid polymer of 0 to 1,000,000 based on the total amount of the resin, and the secondary or / and tertiary amine is 0.01% to 1 equivalent of the carboxyl group of the carboxylic acid polymer. To 1 equivalent, and a photobase generator (a) that generates a base upon irradiation with electromagnetic waves, 0.01 to 0.5 equivalents relative to 1 equivalent of the carboxyl group of the carboxylic acid polymer,
A photosensitive resin composition containing 0.1 to 2 equivalents of a base-base generator (b), in which a base is generated by a base generated from the photobase generator (a), to 1 equivalent of a carboxyl group of the carboxylic acid polymer. Stuff.

(3) The carboxylic acid polymer has the formula [2]

[0019]

[Chemical 12]

(Wherein R ¹ is the same as above, R ² is a carbon atom of 2
The above organic group, R ³ is an organic group having 4 or more carbon atoms, and n
Is an integer) represented by a molecular weight of 10,000 to 1,000
The photosensitive resin composition as described above, which is a carboxylic acid polymer having a molecular weight of 0,000.

(4) The photobase generator (a) has the formula [3]

[0022]

[Chemical 13]

(In the formula, R ⁴ is selected from an organic group having 1 or more carbon atoms, hydrogen and a halogen atom, p is an integer of 0 to 4, R ⁵ and R ⁶ are organic groups having 12 or less carbon atoms, R ⁷ is hydrogen or an organic group having 10 or less carbon atoms).

(5) The base-base generator (b) is
Formula [4]

[0025]

Embedded image

(In the formula, R ⁸ is an organic group having 1 or more carbon atoms or a halogen atom, R ⁹ is an organic group having 1 or more carbon atoms, hydrogen,
Selected from halogen atoms, R ¹⁰ and R ¹¹ are organic groups having 12 or less carbon atoms or hydrogen atoms, and R ¹² and R ¹³ are hydrogen or 1 carbon atoms.
The said photosensitive resin composition represented by 0 or less is an organic group.

(6) The carboxylic acid polymer represented by the above formula [1] or the above formula [2] is added in an amount of 20% by weight or more based on the total amount of the resin, and the secondary or / and tertiary amine is added to the carboxylic acid. 0.0 per 1 equivalent of the carboxyl group of the acid polymer
1 to 1 equivalent and 0.01 to 0.0 of the photobase generator (a) with respect to 1 equivalent of the carboxyl group of the carboxylic acid polymer.
5 equivalents and the base-base generator (b) are added in an amount of 0.1 to 2 with respect to 1 equivalent of the carboxyl group of the carboxylic acid polymer.
A pattern comprising an electrically insulating layer is formed on a substrate including a step of applying a photosensitive resin composition containing an equivalent amount on a substrate and drying, a step of irradiating an electromagnetic wave through a light-shielding mask, and a step of developing with a developing solution. Pattern formation method.

(7) A carboxylic acid polymer having a molecular weight of 10,000 to 1,000,000 represented by the above formula [1] or the above formula [2] is formed on the circuit forming surface or the protective film forming surface of the electronic circuit. 20% by weight or more based on the total amount of resin, 0.01 to 1 equivalent of a secondary or / and tertiary amine to 1 equivalent of a carboxyl group of the carboxylic acid polymer, and a photobase generator (a). Carboxyl group 1 of the carboxylic acid polymer
A photosensitive resin composition containing 0.01 to 0.5 equivalents relative to equivalents and 0.1 to 2 equivalents of the base-base generator (b) relative to 1 equivalent of carboxyl groups of the carboxylic acid polymer is applied. And a step of irradiating with an electromagnetic wave through a light-shielding mask, and a step of developing with a developing solution.

The present invention focuses on the fact that the solubility of the polymer having a carboxylic acid group of the above formula [1] greatly changes due to the presence of a base, and utilizes this. Therefore, any compound having such a carboxylic acid group can be applied.

The molecular weight of the carboxylic acid is preferably 10,000 or more in consideration of the mechanical characteristics of the relief pattern, and is preferably 1,000,000 or less in consideration of solubility in a solvent. .

As the repeating unit of the polymer structure having a carboxylic acid group by chain polymerization, polyacrylic acid and polyacryl described in Table 9.1 of Polymer Data Handbook Basic Edition (Polymer Society of Japan, Baifukan, 1986). Examples thereof include acid alkyl derivatives, maleic acid and its derivatives listed in Table 14.1, fluoroalkyl maleates and vinyl acetate. Further, a polymer of the above monomer or a polymer containing the above monomer as a copolymerization component can be directly applied to the present invention. Even if the monomer is a polymer containing no carboxylic acid group, it can be applied by introducing a carboxylic acid group by chemical modification.

As a typical polymer having a carboxylic acid group, polycondensation type polymers include polyamic acid and chitin. In particular, when the polyamic acid is applied to the present invention, after forming a relief image, by heating or chemically imidizing, by converting into a polyimide, heat resistance,
Relief images with excellent chemical resistance can be obtained, and LSI
It exhibits excellent performance as a protective film, an insulating film for wiring boards, etc.

As the polymer having a carboxylic acid group, particularly by using the carboxylic acid polymer represented by the above formula [2], the effect of the present invention can be more exerted.

The polyamic acid used in the present invention is obtained by reacting a diamine or diisocyanate with a tetracarboxylic acid or its derivative. Examples of tetracarboxylic acid derivatives include acid anhydrides and acid chlorides. It is preferable to use an acid anhydride in terms of reactivity and by-products. Examples of the diamine and acid anhydride derivative used in the present invention include those described in JP-A-61-181829.

The present invention utilizes the fact that the solubility of a polymer having a carboxylic acid group of the above formula [1] in water is greatly improved by the presence of a base. Therefore,
The amine used in the present invention is required to react with the above-mentioned carboxylic acid group to form a salt, and the polymer has water solubility. Examples of such amine compounds include bulky amines such as tertiary alkyl amines, diisopropyl amine and diphenyl amine. Further, when the addition amount is 0.6 to 1 molar equivalent with respect to the carboxylic acid group in the polymer, a good relief pattern is obtained.

The photobase generator (a) for generating a base upon irradiation with the electromagnetic wave is amine cobalt (III) salt,
Examples thereof include compounds such as ammonium carboxylate, sulfonamide, and carbamate. Such compounds include N- [1- (3,5-dimethoxyphenyl) -1-methylethoxycarbonyl] isopropylamine, N-
[(2,6-Dinitrophenyl) methoxycarbonyl] isopropylamine, N- [1- (2,6-dinitrophenyl) ethoxycarbonyl] isopropylamine, N-
[Bis (2,6-dinitrophenyl) methoxycarbonyl] isopropylamine, N- [bis (2-nitrophenyl) methoxycarbonyl] isopropylamine, N-
[(2-Nitrophenyl) methoxycarbonyl] isopropylamine, N- [1- (2-nitrophenyl) ethoxycarbonyl] isopropylamine, N-[(2-nitrophenyl) methoxycarbonyl] piperidine, N, N ′
-Bis [(2-nitrophenyl) methoxycarbonyl]-
1,6-diaminohexane, N- [1- (4,5-dimethyl-2-nitrophenyl) ethoxycarbonyl] isopropylamine, N- [1- (4-methyl-2-nitrophenyl) ethoxycarbonyl] isopropylamine , N
-[1- (6-Methyl-2-nitrophenyl) ethoxycarbonyl] isopropylamine, bromohexaamine cobalt (III) perchlorate, bromohexa (methylamine)
Cobalt (III) perchlorate, chlorohexa (methylamine) cobalt (III) perchlorate, triethylammonium phenylglyoxyate, triethylammonium 2-phenylethenylglyoxyate, N-cyclohexyl-4
-Methylphenyl sulfonamide and the like.

For the synthesis method of these, see J. Am. Che.
m.Soc. 1991, 113, 4303-4313, Fahe
y, JT and Frechet, JMJ (1991) Pro
c.SPIE, 1466, 67, Frechet, JMJ.,
Stanciulescu, M., Lizawa, T., and Willson,
CG, (1989) Proc. ACS Div. Polym.
Mater. Sci. Eng., 60, 170. Graziano, K.
A., Thompson, SD, and Winkle, MR (19
90) Proc. SPIE, 1466, 75. Chem. Mate
r. 1929, 4,453, Wait, S.M. K., Kutal,
C., and Allen, R.A. D., Angew. Makromol Che
m. 1981, 93, 83, Mayer, W., Rudolph,
H. and de Cleur, E. Etc., and can be easily synthesized.

Each of the above-mentioned photobase generators decomposes upon irradiation with light to generate a base. Among these, the photobase generator (a) represented by the above formula [3] has particularly high base generation efficiency and can obtain excellent characteristics. In the formula [3], the group represented by R ⁷ is preferably an organic group having 10 or less carbon atoms in consideration of the film slippage at the time of forming the relief pattern. In addition to the above, the photobase generator used in the present invention may be any as long as it produces a water-soluble amine upon irradiation with electromagnetic waves. Further, in order to obtain water solubility by salt formation, an amine having 12 or less carbon atoms is generally desirable.

As the base-base generator (b) used in the present invention, 1,1-dimethyl-2-cyanoethyl-N-isopropylcarbamate, 1,1-dimethyl-2-phenylethyl-N-isopropylcarbamate, 2 -(9
-Fluorenyl) methyl-N-isopropylcarbamate, 2-methylsulfonylethyl-N-isopropylcarbamate and the like. These are the reaction of the corresponding alcohols with isocyanates in the presence of catalytic amounts of methyllithium (J. Org. Chem. 1990, 55, 59.
19-5922, Cameron, J.F. and Frechet, J.
MJ (1990)) or the reaction of the corresponding alcohol with carbamil chloride.

The present invention can be easily achieved by mixing the polyamic acid synthesized by the above-mentioned known method with the photobase generator (a) and the base-base generator (b). In the present invention, combined use with a triplet sensitizer,
It goes without saying that it can be used in combination with an adhesion improver composed of various amine compounds, a surfactant and the like.

Irradiation with electromagnetic waves or the base generated by the base reacts with the carboxylic acid group in the polymer to change the solubility of the polymer. That is, the portion in which the base and the carboxylic acid react to form a salt has improved solubility in water,
Solubility in organic solvents decreases. This makes it possible to obtain a positive image when an aqueous solvent having a high polarity is used as a developing solution and a negative image when an organic solvent is used as a developing solution.

Since the bond between the carboxylic acid group and the generated base is weak, it is easily eliminated during the imidization process to give a relief pattern of excellent film quality. Since the relief pattern is formed by salt formation, the amount of carboxylic acid in the resin composition is important. When the carboxylic acid content is 20% by weight or more based on all resin components, a good relief pattern is obtained.

The electromagnetic wave has a wavelength of 200.
It is desirable that the thickness is up to 900 nm.

[0044]

[Function] The base-base generator (b) is generated by the base generated by irradiating the photobase generator (a) with an electromagnetic wave.
Then, a base is further generated, and the entire system becomes a base atmosphere in a self-amplifying manner. The carboxylic acid group in the polymer reacts with the generated base to change the solubility in water and enables development with the unexposed area.

The chemical amplification reaction known so far can be applied only to the catalytic reaction, but the self-amplification reaction of the present invention can also be applied to the non-catalytic reaction. Since the bond between the carboxylic acid group and the generated base or between the carboxylic acid group and the base generator is weak, it can be easily desorbed by heating to form a relief pattern having an excellent film quality.

[0046]

【Example】

[Example 1] 1.07 of 2-methyl-1-phenyl-2-propanol (4.51 mg, 30.0 mmol) in ether solution (40 ml) was stirred at room temperature in a nitrogen stream with stirring.
1.40 ml of a prescribed methyllithium ether solution (1.5
0 mmol) is added dropwise. After stirring at room temperature for 5 hours, 2.55 mg (30.0 mmol) of 2-propylisocyanate
Of ether solution (20 ml) is slowly added dropwise. Then, after heating under reflux for 10 hours, it is left to stand until it reaches room temperature.

After distilling off the solvent, chloroform is added, washed with water and brine and dried over magnesium sulfate to remove the solvent. Purified by silica gel column chromatography (hexane / ethyl acetate (1/1)) and recrystallized from a mixed solution of hexane and ethyl acetate to give 1,1-
Dimethyl-2-phenylethyl-N-isopropylcarbamate was obtained.

Oxydiphthalic acid dianhydride (ODPA) and an equivalent amount of diaminodiphenyl ether (DDE) were reacted in N-methyl-2-pyrrolidone to obtain a solid content of 12% by weight.
A polyamic acid solution of In this polyamic acid solution,
2.0 equivalents of triethylamine with respect to ODPA and 0.0.
05 equivalents of N- [1- (4,5-dimethyl-2-nitrophenyl) ethoxycarbonyl] isopropylamine,
2.0 equivalents of 1,1-dimethyl-2-phenylethyl-N
-Isopropylcarbamate was added to obtain a photosensitive resin composition.

This photosensitive resin composition was applied on a glass substrate by a spin coating method, dried at 80 ° C. and exposed with a high pressure mercury lamp through a light shielding mask. When this film was developed in water, a relief pattern could be obtained with almost no contact with the unexposed rear part. 30 more
Heat treatment was performed at 0 ° C. for 1 hour to obtain a tough relief pattern.

Example 2 Instead of 2-methyl-1-phenyl-2-propanol 1 used in Example 1, 1,1 was used.
1-Dimethyl-2-cyanoethyl-N-isopropylcarbamate was synthesized using -dimethyl-2-cyanoethanol.

ODPA was added to the polyamic acid solution of Example 1.
To 2.0 equivalents of triethylamine and 0.05 equivalents of N- [1- (4,5-dimethyl-2-nitrophenyl)
Ethoxycarbonyl] isopropylamine and 2.0 equivalents of 1,1-dimethyl-2-cyanoethyl-N-isopropylcarbamate were added to obtain a photosensitive resin composition.

This photosensitive resin composition was applied on a glass substrate by a spin coating method, dried at 80 ° C. and exposed with a high pressure mercury lamp through a light shielding mask. When this film was developed in water, a relief pattern could be obtained with almost no contact with the unexposed rear part. 30 more
Heat treatment was performed at 0 ° C. for 1 hour to obtain a tough relief pattern.

Example 3 By using 2-methylsulfonylethanol in place of 2-methyl-1-phenyl-2-propanol 1 used in Example 1,
Methylsulfonylethyl-N-isopropylcarbamate was synthesized.

ODPA was added to the polyamic acid solution of Example 1.
To 2.0 equivalents of triethylamine and 0.05 equivalents of N- [1- (4,5-dimethyl-2-nitrophenyl)
Ethoxycarbonyl] isopropylamine and 2.0 equivalents of 2-methylsulfonylethyl-N-isopropylcarbamate were added to obtain a photosensitive resin composition. This photosensitive resin composition was applied onto a glass substrate by spin coating, dried at 80 ° C., and exposed with a high pressure mercury lamp through a light shielding mask. When this film was developed in water, a relief pattern could be obtained with almost no contact with the unexposed rear part. Further, it was heat-treated at 300 ° C. for 1 hour to obtain a tough relief pattern.

Example 4 By using 9-fluorenylmethanol in place of 2-methyl-1-phenyl-2-propanol 1 used in Example 1, 9-fluorenylmethyl-N-isopropyl was obtained. Carbamate was synthesized.

ODPA was added to the polyamic acid solution of Example 1.
To 2.0 equivalents of triethylamine and 0.05 equivalents of N- [1- (4,5-dimethyl-2-nitrophenyl)
Ethoxycarbonyl] isopropylamine and 2.0 equivalents of 9-fluorenylmethyl N-isopropylcarbamate were added to obtain a photosensitive resin composition. This photosensitive resin composition was applied onto a glass substrate by spin coating, dried at 80 ° C., and exposed with a high pressure mercury lamp through a light shielding mask. When this film was developed in water, a relief pattern could be obtained with almost no contact with the unexposed rear part. Further, it was heat-treated at 300 ° C. for 1 hour to obtain a tough relief pattern.

Example 5 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and an equivalent amount of diaminodiphenyl ether (DDE) were reacted in N-methyl-2-pyrrolidone to give a solid. A 12% by weight polyamic acid solution was obtained. To this polyamic acid solution, 2.0 equivalents of triethylamine and 0.05 equivalents of N relative to ODPA were added.
-[1- (4,5-Dimethyl-2-nitrophenyl) ethoxycarbonyl] isopropylamine and 2.0 equivalents of 1,1
-Dimethyl-2-phenylethyl-N-isopropylcarbamate was added to obtain a photosensitive resin composition. This photosensitive resin composition was applied onto a glass substrate by spin coating, dried at 80 ° C., and exposed with a high pressure mercury lamp through a light shielding mask. When this film was developed in water,
The relief pattern could be obtained with almost no contact with the unexposed rear part. Further heat treatment at 300 ℃ for 1 hour,
A strong relief pattern was obtained.

Example 6 The same experiment as in Example 1 was carried out by changing the developing solution to NMP, and as a result, a relief pattern could be obtained with almost no contact with the exposed dew part. Further, it was heat-treated at 300 ° C. for 1 hour to obtain a tough relief pattern.

Example 7 A buffer coat film was formed in the same manner as in Example 1 by applying the photosensitive resin composition of Example 1 onto a silicon wafer on which wiring of an LSI was completed and exposing it. Since no organic solvent is used in the developer, the waste solvent treatment can be greatly reduced. After the obtained LSI chip was molded, a solder heat resistance test was carried out. As a result, no bulge was observed and an LSI package having excellent heat resistance was obtained.

Example 8 A buffer coat film was formed in the same manner as in Example 7, except that the developing solution was changed to NMP. At this time, the mask used was the one used in Example 7 and the one used in negative or positive inversion. After molding the obtained LSI chip, a solder heat resistance test was conducted. As a result, no bulge was observed and an LSI package having excellent heat resistance was obtained.

[0061]

EFFECT OF THE INVENTION The positive type photosensitive resin composition of the present invention, which can be developed with an aqueous solvent, can provide a highly sensitive relief pattern without causing environmental pollution or working environment.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical indication location H01L 21/312 B (72) Inventor Yoshiaki Okabe 7-1 Omika-cho, Hitachi-shi, Ibaraki Hitachi Ltd. Hitachi, Ltd. (72) Inventor, Mina Ishida, 7-1, 1-1, Omika-cho, Hitachi, Hitachi, Ltd. Hitachi, Ltd., Hitachi, Ltd. (72) Toshinori Hirano, 7-1, 1-1, Omika, Hitachi, Ibaraki Hitachi, Ltd., Hitachi Research Laboratory

Claims (13)

[Claims] 1. A photosensitive resin composition comprising a substance that generates a base upon irradiation of electromagnetic waves, a substance that generates a base by the base, and a polymer compound whose polarity is changed by the base. 2. A formula [1]: (In the formula, A is an organic group having 2 or more carbon atoms, n is an integer, and R ¹
Is an organic group having 1 or more carbon atoms, a hydrogen atom, or a halogen atom), and has a molecular weight of 10,000 to 1,000.
20 carboxylic acid polymer based on total resin amount
% Or more, and secondary or / and tertiary amine is used in an amount of 0.0 with respect to 1 equivalent of the carboxyl group of the carboxylic acid polymer.
1 to 1 equivalent, and a photobase generator (a) that generates a base upon irradiation with electromagnetic waves, 0.01 to 0.5 equivalents relative to 1 equivalent of a carboxyl group of the carboxylic acid polymer, and the photobase generator. A photosensitive resin composition, characterized in that the base-base generator (b), in which a base is generated by the base generated in (a), is contained in an amount of 0.1 to 2 equivalents relative to 1 equivalent of a carboxyl group of the carboxylic acid polymer. Stuff. 3. The carboxylic acid polymer has the formula [2]: (In the formula, R ¹ is an organic group having 1 or more carbon atoms, a hydrogen atom or a halogen atom, R ² is an organic group having 2 or more carbon atoms, R ³
Is an organic group having 4 or more carbon atoms and n is an integer), and the photosensitive resin composition according to claim 2, which is a carboxylic acid polymer having a molecular weight of 10,000 to 1,000,000. 4. The photobase generator (a) is represented by the formula [3]: (In the formula, R ⁴ is selected from an organic group having 1 or more carbon atoms, hydrogen and a halogen atom, p is an integer of 0 to 4, R ⁵ and R ⁶ are organic groups having 12 or less carbon atoms, and R ⁷ is Hydrogen or carbon number 10
The photosensitive resin composition according to claim 2, which is represented by the following organic group). 5. The photosensitive resin composition according to claim 2, wherein the photobase generator (a) is at least one selected from cobalt (III) amine salts, ammonium carboxylic acid salts, and sulfonamides. 6. The base-base generator (II) has the formula [4]: (In the formula, R ⁸ is an organic group having 1 or more carbon atoms or a halogen atom, R ⁹ is selected from an organic group having 1 or more carbon atoms, hydrogen and a halogen atom, and R ¹⁰ and R ¹¹ are organic groups having 12 or less carbon atoms. Or a hydrogen atom, R ¹² and R ¹³ are each a hydrogen atom or an organic group having 10 or less carbon atoms). 7. A formula [1]: (In the formula, A is an organic group having 2 or more carbon atoms, n is an integer, and R ¹
Is an organic group having 1 or more carbon atoms, a hydrogen atom, or a halogen atom), and has a molecular weight of 10,000 to 1,000.
20 carboxylic acid polymer based on total resin amount
% Or more, and secondary or / and tertiary amine is used in an amount of 0.0 with respect to 1 equivalent of the carboxyl group of the carboxylic acid polymer.
1 to 1 equivalent, and a photobase generator (a) that generates a base upon irradiation with electromagnetic waves, 0.01 to 0.5 equivalents relative to 1 equivalent of a carboxyl group of the carboxylic acid polymer, and the photobase generator. The photosensitive resin composition containing 0.1 to 2 equivalents of the base-base generator (b), in which a base is generated by the base generated in (a), per 1 equivalent of the carboxyl group of the carboxylic acid polymer, A pattern forming method for forming a pattern made of an electrically insulating layer on a substrate, which comprises a step of coating and drying on the substrate, a step of irradiating an electromagnetic wave through a light-shielding mask, and a step of developing with a developing solution. 8. The carboxylic acid polymer of the photosensitive resin composition has the formula [2]: (In the formula, R ¹ is an organic group having 1 or more carbon atoms, a hydrogen atom or a halogen atom, R ² is an organic group having 2 or more carbon atoms, R ³
Is an organic group having 4 or more carbon atoms, and n is an integer), and is a polymer having a molecular weight of 10,000 to 1,000,000. 9. The photobase generator (a) of the photosensitive resin composition is represented by the formula [3]: (In the formula, R ⁴ is selected from an organic group having 1 or more carbon atoms, hydrogen and a halogen atom, p is an integer of 0 to 4, R ⁵ and R ⁶ are organic groups having 12 or less carbon atoms, R ⁷ is hydrogen or The method for forming a pattern according to claim 7, wherein the pattern forming method is represented by an organic group having 10 or less carbon atoms. 10. The base-base generator (b) of the photosensitive resin composition is represented by the formula [4]: (In the formula, R ⁸ is an organic group having 1 or more carbon atoms or a halogen atom, R ⁹ is selected from an organic group having 1 or more carbon atoms, hydrogen and a halogen atom, and R ¹⁰ and R ¹¹ are organic groups having 12 or less carbon atoms. Or a hydrogen atom, R ¹² and R ¹³ are represented by hydrogen or an organic group having 10 or less carbon atoms). 11. The electromagnetic wave has a wavelength of 200 to 900 n.
The pattern forming method according to any one of claims 7 to 10, wherein m is m. 12. A circuit-forming surface or a protective-film-forming surface of an electronic circuit has the formula [1]: (In the formula, A is an organic group having 2 or more carbon atoms, n is an integer, and R ¹
Is an organic group having 1 or more carbon atoms, a hydrogen atom, or a halogen atom), and has a molecular weight of 10,000 to 1,000.
20 carboxylic acid polymer based on total resin amount
% Or more, and secondary or / and tertiary amine is used in an amount of 0.0 with respect to 1 equivalent of the carboxyl group of the carboxylic acid polymer.
1 to 1 equivalent, and a photobase generator (a) that generates a base upon irradiation with electromagnetic waves, 0.01 to 0.5 equivalents relative to 1 equivalent of a carboxyl group of the carboxylic acid polymer, and the photobase generator. A step of coating a photosensitive resin composition containing the base-base generator (b) in an amount of 0.1 to 2 equivalents with respect to 1 equivalent of a carboxyl group of the carboxylic acid polymer with the base generated in (a) and drying, A method for manufacturing an electronic device, which comprises a step of irradiating an electromagnetic wave through a conductive mask and a step of developing with a developing solution. 13. The carboxylic acid polymer has the formula [2]: (In the formula, R ¹ is an organic group having 1 or more carbon atoms, a hydrogen atom or a halogen atom, R ² is an organic group having 2 or more carbon atoms, R ³
Is an organic group having 4 or more carbon atoms, and n is an integer), and is a polymer having a molecular weight of 10,000 to 1,000,000.