JP2002162743A - Photosensitive resin composition and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyimide precursor which can be developed in an alkaline aqueous solution to form a sharp negative pattern. SOLUTION: A photosensitive resin composition consisting of (A) a polyimide precursor containing a phenolic OH group in its ester structure, (B) a compound containing an aromatic nucleous structure substituted with acetoxymethyl groups such as di(acetoxymethyl)benzene which works as an insolubilizor of the polyimide precursor (A) in an alkaline aqueous solution, (C) a photo-acid generator which generates an acidic functional group by an irradiation with an active light, and (D) a solvent and a manufacturing method for the photosensitive resin including a preparation process of a resin solvent adding the photo-acid generator and the insolubilizor to the polyimide precursor are presented.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide-based photosensitive resin composition used as an electric or electronic insulating material in the production of semiconductor devices and the like, and a method for producing the same. Things are
The present invention is applied to an insulating protective film formed on a semiconductor element such as an IC or an LSI which requires processing of a fine pattern.

[0002]

2. Description of the Related Art In recent years, polyimide resins have been developed in the fields of electricity and electronics, including semiconductors, due to their high heat resistance, chemical resistance, electrical insulation, low dielectric constant, and the like. , IC, LSI and VLSI chips are used as interlayer insulating films and surface protective films. However, in the conventional method of forming a polyimide film pattern, a polyimide precursor must be applied on a wafer and dried, and then pattern etching must be performed using a photoresist. It had to be used as an etchant.

[0003] For this reason, attempts to introduce a photosensitive group into a polyimide precursor to enable the formation of a pattern of the polyimide itself have been made by various material manufacturers, and have come to a practical stage in some product fields. However, photosensitive polyimides currently in practical use can be broadly classified into those in which photosensitive groups are introduced into the polyimide precursor by ionic bonds and those in which photosensitive groups are introduced through ester bonds. The sensitivity is low (the solubility difference is low) with respect to the ultraviolet rays used in the above, and the process margin is low because the solubility of the resin is reduced in the process. In the latter, a complicated process is required in the production stage, and a product having a molecular weight sufficient for practical use cannot be obtained. Furthermore, these resins adopt a negative pattern forming method,
At the time of pattern formation, development must be performed with an organic solvent, which is a serious problem from the viewpoint of environmental conservation.
From these problems, there is a strong demand for a negative photosensitive polyimide precursor that can use an aqueous alkaline solution at the time of pattern formation, and that does not swell in the developer and that can achieve high resolution.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional disadvantages and to provide a polyimide precursor having a negative pattern forming ability which can be developed with an alkaline aqueous solution, and to stabilize the polyimide precursor. It is intended to provide a manufacturing method.

[0005]

Means for Solving the Problems As a result of intensive research aimed at achieving the above object, the present inventor has found that the above object can be achieved by employing a resin composition described below and a method for producing the same. The present invention has been completed.

That is, the photosensitive resin composition of the present invention comprises:
(A) a polyimide precursor having the following repeating units:

Embedded image (Wherein, R ¹ is a tetravalent aromatic group, a tetravalent organic group in which a plurality of aromatic rings are single-bonded, or a group in which a plurality of aromatic rings are -O-, -CO-, -SO ₂ -, - CH ₂ - or -
A tetravalent organic group linked by C (CF ₃ ) ₂ —,
² is a divalent aromatic group, a divalent organic group in which a plurality of aromatic rings are single-bonded, or a group in which a plurality of aromatic rings are -O-, -CO
_{-, - SO 2 -, -} CH 2 - or -C (CF _{3) 2}
And a divalent organic group linked by — and R ³ , R ⁴
Is a residue of an aromatic compound having a phenolic OH group. (B) A compound containing an acetoxymethyl group-substituted aromatic ring structure, wherein the (A) polyimide precursor is insolubilized in an aqueous alkali solution. It is characterized by comprising an insolubilizing agent, (C) a photoacid generator that generates an acidic functional group by actinic rays, and (D) a solvent.

Further, the method for producing the photosensitive resin composition of the present invention comprises: (1) an ester of an acid component having an R ¹ skeleton and an alcoholic compound having an R ³ or R ⁴ skeleton shown in the following repeating unit: Reaction step,

Embedded image (Wherein, R ¹ is a tetravalent aromatic group, a tetravalent organic group in which a plurality of aromatic rings are single-bonded, or a group in which a plurality of aromatic rings are -O-, -CO-, -SO ₂ -, - CH ₂ - or -
A tetravalent organic group linked by C (CF ₃ ) ₂ —,
² is a divalent aromatic group, a divalent organic group in which a plurality of aromatic rings are single-bonded, or a plurality of aromatic rings is a single bond, -O-,
_{-CO -, - SO 2 -,} - CH 2 - or -C (CF
_{3) 2} - is a bivalent aromatic radical which is bound by, and R
⁽³⁾ R ⁴ is a residue of an aromatic compound having a phenolic OH group. (2) Under the addition of a dehydrating condensing agent, the esterification reaction product of (1) and R ² in the above formula 4 A polycondensation reaction step with a diamine compound serving as a skeleton, (3) a purification step of a polyimide precursor subjected to the polycondensation reaction, and (4) preparation of a resin solvent containing a photoacid generator of (C) and an insolubilizing agent of (B). It is characterized by comprising a process.

Hereinafter, the present invention will be described in detail.

First, the method for producing the photosensitive resin composition of the present invention will be described in the order of the steps (1) to (4), and simultaneously, the components (A) to (D) of the photosensitive resin composition of the present invention will be described. explain.

(1) An esterification reaction step between an acid component such as an acid dianhydride having an R ¹ skeleton and an alcoholic compound having an R ³ or R ⁴ skeleton in the formula (4) ^{As an} acid component having ^one skeleton, for example, pyromellitic acid, 3,3 ′, 4,
4'-biphenyltetracarboxylic acid, 2,3,3 ',
4'-biphenyltetracarboxylic acid, 3,3 ', 4
4'-benzophenonetetracarboxylic acid, 4,4'-oxydiphthalic acid, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,3
6,7-naphthalenetetracarboxylic acid, 1,2,5,6
-Naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,4 , 5-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3,3 ', 4,4'-bicyclohexyltetracarboxylic acid, 2,3,5-tricarboxycyclopentylacetic acid, , 4-Dicarboxy-1,2,3,4-tetrahydronaphthalene-1-succinic acid and its anhydrides, which can be used alone or in combination.

Further, examples of the alcohol compounds having R ³ and R ⁴ skeletons to be introduced into the acid component serving as the R ¹ skeleton through an ester bond include, for example, 2-hydroxybenzyl alcohol, 3-hydroxybenzyl alcohol, and 4-hydroxybenzyl alcohol. Alcohol, 3,5-dihydroxybenzyl alcohol, 2- [bis (4-hydroxyphenyl)
Methyl] benzyl alcohol, hydroquinone, hydroxyhydroquinone, 4-hydroxy-3-methoxybenzyl alcohol, bis (4-hydroxy-3-methylphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, etc., alone or in combination of two or more These can be used in combination.

The acid component serving as the R ¹ skeleton and the R ³ , R
The esterification reaction of a compound having a ⁴ skeleton is, for example, an acid dianhydride having an R ¹ skeleton and an alcoholic compound having an R ³ , R ⁴ skeleton. Solvent, for example N-methyl-2-
It is preferable to carry out the reaction at room temperature in the presence of a basic catalyst such as triethylamine, pyridine, triethanolamine or the like for smoothly performing the reaction using pyrrolidone or the like. This basic catalyst is 1.5 to 3.0 times the mol of the acid component,
Preferably, it can be used in a range of 2.0 to 2.5 moles.

(2) Polycondensation reaction step of the above ester compound and a diamine compound serving as the R ² skeleton in the above formula (6) As the diamine compound serving as the R ² skeleton used in the present invention, for example, m-phenylene Diamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminotoluene, 1-methoxy-2,4-diaminobenzene, 1,4- Diamino-2-methoxy-5-methylbenzene, 1,3-diamino-4,6-dimethylbenzene,
1,2-diaminonaphthalene, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, ,
6-diaminonaphthalene, 1,4-diamino-2-methylnaphthalene, 1,5-diamino-2-methylnaphthalene, 1,3-diamino-2-phenylnaphthalene, 2,
2-bis (4-aminophenyl) propane, 1,1-bis (4-aminophenyl) ethane, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-Tetramethyl-4,4'-diaminodiphenylmethane, 3,
3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 4,4'
-Methylenebis (cyclohexylamine), 4,4'-
Methylene bis (3,3-dimethyl-cyclohexylamine), 2,4'-diaminodiphenyl sulfide, 4,
4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminobenzanilide,
3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, bis (4-aminophenyl) diethylsilane, bis (4-aminophenyl) diphenylsilane,
Bis (4-aminophenyl) -N-methylamine, bis (4-aminophenyl) -N-phenylamine, 3,
3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,6-diaminopyridine, 3,5-diaminopyridine, 4,4'-diaminobiphenyl,
3'-diaminobiphenyl, 3,3'-dimethyl-4,
4'-diaminobiphenyl, 3,3'-dimethoxy-
4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, o-toluidinesulfone, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-
Aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 9,9- Bis (4-aminophenyl) fluorene, 2,2-bis (4
-Aminophenyl) hexafluoropropane, 2,2-
Bis (3-aminophenyl) hexafluoropropane,
1,1-bis (4-aminophenyl) -1-phenyl-
2,2,2-trifluoroethane, 2,2-bis (3-
Amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2-bis [4- (4
-Aminophenoxy) phenyl] hexafluoropropane and the like, and these can be used alone or as a mixture of two or more. These compounds are preferably used in an equimolar amount with respect to the acid dianhydride having an R ¹ skeleton.
It can be used in the range of 1.5 moles.

Next, the dehydrating condensing agent used in the above polycondensation reaction in the present invention will be described.

When the acid component of the esterification reaction product and the diamine component are reacted by the polycondensation method, the reaction is usually carried out using an acid chloride. However, in the electric and electronic fields including semiconductor devices, the reaction is carried out. Since liberated chloride ions cause poor product reliability, it is necessary to sufficiently wash with pure water after polycondensation when performing polymerization by an acid chloride method. As another polycondensation method, a carbodiimide derivative such as DCC (dicyclohexylcarbodiimide) which is a dehydration condensing agent can be used.
There are problems such as simultaneous side reactions, gelation of the polyimide precursor, toxicity, and the like, and it is difficult to completely remove urea generated as a by-product. For this reason, it is necessary to cool the reaction system, add the dehydrating condensing agent in several portions, or break the molar balance between the acid component and the diamine component before use. As another method, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazole) phosphonate and its derivative, diphenyl (2,3 -Dihydro-2-thioxo-3-benzothiazole) phosphonate and a derivative thereof, and this method enables stable production under mild conditions, and therefore has high resolution and high film properties. Can be obtained. These can be used alone or in combination of two or more. These can be used in an amount of 1 to 3 moles, preferably 2 to 2.5 moles, per 1 mole of the ester compound.

As the solvent for the polycondensation reaction of the polyimide precursor used in the present invention, for example, N-methylpyrrolidone,
An aprotic polar solvent such as N, N'-dimethylacetamide and N, N'-dimethylformamide, cyclohexanone, cyclopentanone and the like are used, and these can be used alone or as a mixture of two or more.

(3) Step of Purifying Polyimide Precursor After Polycondensation Reaction The obtained slurry polymer is treated with methanol, ethanol,
After stirring and washing in a poor solvent such as isopropyl alcohol and water, the precipitate is dried under reduced pressure to obtain the polyimide precursor [component (A)] represented by Chemical Formula 3 described above.

(4) Step of Preparing Polyimide Precursor Solution Containing Photoacid Generator [Component C] and Insolubilizer [Component B] A compound [(C) which can be used in the present invention and is generally called a photoacid generator ) Component] is a substance that generates a Lewis acid or a cationic species by actinic rays such as ultraviolet rays, and is often used in recent years as a resist for fine pattern formation (commonly called a chemically amplified resist) of a semiconductor integrated circuit. Specifically as the photoacid generator, for example,

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Embedded image And the like, and these can be used alone or in combination of two or more.

These compounds are preferred as the photoacid generator used in the present invention, but are not limited to the above structure as long as they can be decomposed by irradiation with ultraviolet rays to efficiently generate an acid. Absent. The compounding ratio of the [(C) component] called a photoacid generator is preferably 0.1 to 20 parts by weight. If the amount is less than 0.1 part by weight, the sensitivity to ultraviolet rays is low, and if it exceeds 20 parts by weight, the properties of the obtained coating film are deteriorated.

The insolubilizer added to the polyimide precursor solution together with the photoacid generator is a compound containing an acetoxymethyl group-substituted aromatic ring structure, and may be one represented by the following general formula.

[0021]

Embedded image In the above formula, R ⁵ is a mono-, di- or trivalent aromatic group, R ⁶
It represents a single bond to the acetoxymethyl group-substituted aromatic ring, -O -, - CO -, - CH 2, -SO 2 -, - NH
Is a 1, 2, 3 or tetravalent organic group including-, etc., m represents an integer of 1 to 3, and n represents an integer of 1 to 4, respectively.

Specific compounds having an R ⁵ skeleton include:

Embedded image And specific compounds having an R ⁵ skeleton include:

Embedded image Is mentioned.

These compounds are more preferable in the present invention, but are not limited to the above compounds as long as they have an aromatic ring structure having one or more acetoxymethyl groups. When used, they can be used alone or as a mixture of two or more kinds, and the added amount is preferably 1 to 10 parts by weight. If the amount exceeds 10 parts by weight, the properties of the coating film obtained will be reduced.

The resin composition obtained according to the present invention is used in the form of being dissolved in a solvent. Examples of the solvent [component (D)] used for dissolution include N-methylpyrrolidone, N, N'-dimethylacetamide, N,
Aprotic polar solvents such as N'-dimethylformamide; cyclohexanone, cyclopentanone, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, and the like. Alternatively, two or more kinds can be used in combination.

Next, a method of using the resin composition of the present invention will be described.

When application to a semiconductor device is considered, first, the resin composition is coated on a target wafer using a spin coater, and then the coating film is dried at 90 to 130 ° C. An active ultraviolet ray having a wavelength of 365 nm or 436 nm is irradiated through a mask having a pattern drawn on the obtained coating film. In order to insolubilize the acid generated from the photoacid generator by this exposure and the compound having an acetoxymethyl group-substituted aromatic ring structure, 90 to 90%
The heat treatment is performed again at 120 ° C. Next, this coating film is coated with an aqueous alkali solution, for example, an aqueous solution of an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, or the like, a primary amine such as ethylamine or n-propylamine, diethylamine, di-n-propyl. Secondary amines such as amines, tertiary amines such as triethylamine and methyldimethylamine, dimethylethanolamine,
An alcohol amine such as triethanolamine, or a quaternary amine such as tetramethylammonium hydroxide or tetraethylammonium hydroxide is used to dissolve and develop only the unirradiated portion with active light, and then rinsed with pure water. As a developing system, a system such as spray, paddle, immersion, and ultrasonic wave can be considered. Thus, a desired negative pattern can be obtained on the target wafer. Furthermore, by heat-treating the coating film, the resin composition is imidized, and a negative pattern of a polyimide film having excellent film properties can be formed.

[0027]

The most significant feature of the present invention is that the following negative pattern formation mechanism has been discovered. In the resin composition of the present invention, the substrate is subjected to a spin coating drying step on the substrate, and then the coating is irradiated with an actinic ray such as an ultraviolet ray to decompose the photoacid generator in the actinic ray irradiating portion, thereby producing an acid. Occurs. Furthermore the acid generated by heating in the next step of the general formula polymer having phenolic OH groups R ^3, R ⁴ to R ^1, R ² backbone, R ^3, R
⁴ chemically reacts with an acetoxymethyl group-substituted aromatic compound having an R ⁵ or R ⁶ skeleton to become insoluble in an aqueous alkali solution. The R ³ and R ⁴ sites of this polymer are soluble in aqueous alkaline solutions,
Only the part irradiated with active light such as ultraviolet rays is insolubilized and does not dissolve, and the unirradiated part shows solubility in an alkaline aqueous solution. Because of this high contrast, the photosensitive resin composition of the present invention can form a negative pattern having high resolution and good dimensional control.

[0028]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be specifically described based on embodiments.

Example 1 1 mol of benzophenonetetracarboxylic dianhydride, 10 L of N-methyl-2-pyrrolidone and 2.1 mol of 4-hydroxybenzyl alcohol were added to a reaction flask equipped with a nitrogen inlet tube and stirred. Followed by 2.1 mol
Of triethylamine is added dropwise over 30 minutes. This state was left for 3 hours. To this, 1 mol of 4,4'-diaminodiphenyl ether was added, and the mixture was stirred for 30 minutes.
l of diphenyl (2,3-dihydro-2-thioxo-3
-Benzoxazole phosphonate is added in five portions, and a condensation reaction is carried out for 5 hours in that state. The obtained slurry mixture is poured into a large amount of methanol for washing, and the obtained solid resin is dried by a vacuum dryer for 12 hours. Further, 30 g of the dried solid resin, 10 g of di (acetoxymethyl) benzene and 2.0 g of 1,8-naphthalimidyl triflate were dissolved in 70 g of N-methyl-2-pyrrolidone, and the obtained slurry was 1 μm After filtration, Sample 1 was obtained.

This sample 1 was coated on a 6-inch silicon wafer using a spin coater and dried by heating at 100 ° C. for 3 minutes on a bake plate to form a film having a thickness of 10 μm.
m was obtained. This coating film was 300 m thick by an ultraviolet exposure machine using a filter that transmits only 365 nm.
The test pattern was irradiated with an energy of j / cm ² , and subsequently heated at 100 ° C. for 1 minute on a baking plate.
Paddle development was performed with a 38% aqueous solution of TMAH (tetramethylammonium hydride) for 1 minute. By this operation, a negative relief pattern in which the portion other than the UV-irradiated portion of the coating film was dissolved was obtained. Observation of the obtained pattern with an optical microscope confirmed that a pattern up to 5.0 μm was formed sharply.

Further, this pattern was subjected to a heat treatment at 150 ° C. for 1 hour, then at 250 ° C. for 1 hour, and further at 350 ° C. for 1 hour to complete the imidization of the coating film. This imide pattern was firmly adhered to the silicon wafer, and no resin crack or peeling was observed in the pattern.

Example 2 In a reaction flask equipped with a nitrogen inlet tube, 1 mol of 2,2'-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 10 L of N-methyl-2-pyrrolidone, -Hydroxybenzyl alcohol 2.1mo
and stirring, followed by dropwise addition of 2.1 mol of triethylamine over 30 minutes. This state was left for 3 hours. 4,4'-diaminodiphenylsulfone 1
After stirring for 30 minutes, 2.1 mol of diphenyl (2,3-dihydro-2-thioxo-3-benzoxazole) phosphonate is added in five portions, and a condensation reaction is performed for 5 hours in that state. The obtained slurry mixture is poured into a large amount of methanol for washing, and the obtained solid resin is dried by a vacuum dryer for 12 hours. Further, 30 g of the dried solid resin, 10 g of di (acetoxymethyl) benzene and 2.0 g of 1,8-naphthalimidyl triflate were dissolved in 70 g of N-methyl-2-pyrrolidone, and the obtained slurry was filtered by 1 μm. Thus, Sample 2 was obtained.

Sample 2 was coated on a 6-inch silicon wafer using a spin coater and dried by heating at 100 ° C. for 3 minutes on a baking plate to form a film having a thickness of 10 μm.
m was obtained. This coating film was 300 m thick by an ultraviolet exposure machine using a filter that transmits only 365 nm.
The test pattern was irradiated with an energy of j / cm ² , and subsequently heated at 100 ° C. for 1 minute on a baking plate.
Paddle development was performed with a 38% aqueous solution of TMAH (tetramethylammonium hydride) for 1 minute. By this operation, a negative relief pattern in which the portion other than the UV-irradiated portion of the coating film was dissolved was obtained. Observation of the obtained pattern with an optical microscope confirmed that a pattern up to 5.0 μm was formed sharply.

Further, this pattern was subjected to a heat treatment at 150 ° C. for 1 hour, then at 250 ° C. for 1 hour, and further at 350 ° C. for 1 hour to complete the imidization of the coating film. This imide pattern was firmly adhered to the silicon wafer, and no resin crack or peeling was observed in the pattern.

[0035]

The present invention is a photosensitive polyimide precursor having a negative pattern forming ability, and an alkaline aqueous solution can be used for pattern formation. For this reason, not only can the obtained pattern swell little in the developing solution, and not only can a very sharp high-resolution pattern be obtained, but also industrial waste of organic solvents that has been generated in large quantities can be completely eliminated. Further, the polyimide coating finally obtained is excellent in heat resistance and chemical resistance, so that it can be used in the same manner as a commonly used semiconductor device protective film. The present invention relates to the resin skeleton itself used in the photosensitive resin composition and a method for producing the resin skeleton, but these are based on a completely new idea, and are very unique inventions like no other. It is easy to understand.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 503 G03F 7/004 503Z H01L 21/027 H01L 21/312 B 21/312 21/30 502R F Term (Reference) 2H025 AA03 AB16 AC01 AD01 BE00 BE07 CB25 CB45 CC03 CC20 FA17 4J002 CM041 EE037 EH037 EH157 EP017 EU027 EV206 EV246 EV256 EV296 EY026 FD146 FD207 GP03 HA08 4J043 PA02 PA19 QB31 RA35 SA47 SA42 TA42 SA43 TA71 UA011 UA041 UA042 UA121 UA122 UA131 UA132 UA141 UA261 UA262 UA331 UB011 UB012 UB061 UB062 UB121 UB122 UB151 UB241 UB281 UB301 UB302 VA011 VA012 VA021 VA022 VA031 VA032 VA041 VA042 VA051 VA052 VA061 VA062 VA081 VA082 YA01 YA02 YA03 YA06 YA08 ZA46 ZB22 ZB50 5F058 AC02 AC06 AC07 AF04 AG01 AH01

Claims (2)

[Claims] (A) a polyimide precursor having the following repeating unit: (Wherein, R ¹ is a tetravalent aromatic group, a tetravalent organic group in which a plurality of aromatic rings are single-bonded, or a group in which a plurality of aromatic rings are -O-, -CO-, -SO ₂ -, - CH ₂ - or -
A tetravalent organic group linked by C (CF ₃ ) ₂ —,
² is a divalent aromatic group, a divalent organic group in which a plurality of aromatic rings are single-bonded, or a group in which a plurality of aromatic rings are -O-, -CO
_{-, - SO 2 -, -} CH 2 - or -C (CF _{3) 2}
And a divalent organic group linked by — and R ³ , R ⁴
Is a residue of an aromatic compound having a phenolic OH group. (B) A compound containing an acetoxymethyl group-substituted aromatic ring structure, wherein the (A) polyimide precursor is insolubilized in an aqueous alkali solution. A photosensitive resin composition comprising: an insolubilizer; (C) a photoacid generator that generates an acidic functional group by actinic rays; and (D) a solvent. 2. (1) R ¹ shown in the following repeating unit
An esterification reaction step between an acid component having a skeleton and an alcoholic compound having R ³ and R ⁴ skeletons, (Wherein, R ¹ is a tetravalent aromatic group, a tetravalent organic group in which a plurality of aromatic rings are single-bonded, or a group in which a plurality of aromatic rings are -O-, -CO-, -SO ₂ -, - CH ₂ - or -
A tetravalent organic group linked by C (CF ₃ ) ₂ —,
² is a divalent aromatic group, a divalent organic group in which a plurality of aromatic rings are single-bonded, or a group in which a plurality of aromatic rings are -O-, -CO
_{-, - SO 2 -, -} CH 2 - or -C (CF _{3) 2}
And a divalent organic group linked by — and R ³ , R ⁴
Is a residue of an aromatic compound having a phenolic OH group. (2) With the addition of a dehydrating condensing agent, the esterification reaction product of (1) and a diamine compound serving as an R ² skeleton in Formula 2 (3) a step of purifying the polyimide precursor subjected to the polycondensation reaction, and (4) a step of preparing a resin solvent containing the photoacid generator (C) and the insolubilizing agent (B). A method for producing a photosensitive resin composition, comprising: