JP2000273172A - Polyamic ester, its production, photopolymer composition, production of pattern therefrom, and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyamic ester which can give a photopolymer composition developable with an aqueous liquid and capable of forming a high-resolution pattern after being developed by reacting a tetracarboxylic dianhydride with an alcohol under specified conditions, further reacting the reaction product with a halogenating agent to convert it into an active species, and reacting this species with a diamine. SOLUTION: An alcohol having a carbon-carbon double bond is reacted with a tetracarboxylic dianhydride in the presence of a basic catalyst having a pKb of 7 or below at 25 deg.C to synthesize a dicarboxylic diester. This ester is converted into an active species, and the species is reacted with a diamine component containing a diamine having an acidic group to obtain a polyamic ester having a structure of desirably, formula I or II. In the formulae, R1 and R4 are each a tetravalent organic group; R2 is a trivalent or tetravalent organic group; the two R3s and the two R5s are each an organic group having a carbon- carbon double bond; A is an acidic group; (n) is 1 or 2; and R6, R7, R8, and R9 are each H or a monovalent organic group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide acid ester suitable as a material for a protective film such as a surface coat film of a semiconductor element or an interlayer insulating film of a thin-film multilayer wiring board, a method for producing the same, and a photosensitive resin containing the same. The present invention relates to a composition, a method for producing a pattern, and an electronic component.

[0002]

2. Description of the Related Art Conventionally, as a photosensitive resin composition using a polyimide precursor, an aromatic tetracarboxylic dianhydride described in JP-B-5-67026 is reacted with an olefinically unsaturated alcohol. Olefin aromatic tetracarboxylic acid diester, and the resulting compound and diamine are polymerized by a dehydration condensation reaction using carbodiimides, containing a polyimide precursor having a photosensitive group introduced by a covalent bond, JP-B-63-31939. JP-A No. 2000-205, and a polyamide acid obtained by reacting an aromatic tetracarboxylic dianhydride with an aromatic diamine, an amine compound having a photosensitive group is ion-bonded, and a photosensitive group is introduced. ing.

[0003] Each of these is applied to a substrate in the form of a varnish dissolved in an appropriate organic solvent, dried to form a film, and then irradiated with ultraviolet rays through an appropriate photomask to cure the exposed portion by photocuring. Type photosensitive composition, which is developed and rinsed with an organic solvent to form a relief /
That's what gets the pattern.

However, when an organic solvent is used as a developing solution at the time of pattern formation, swelling of an exposed portion tends to occur at the time of development, and it is difficult to obtain a high-resolution pattern.
In addition, when an organic solvent is used, there is also a problem that the health of workers is adversely affected and waste liquid treatment is troublesome.

Therefore, as a material which can be developed with an aqueous liquid, which solves the above problems, for example, a positive polymer in which a naphthoquinonediazidosulfonylamide group is introduced into a carboxyl group of polyamic acid has been proposed ( JP-A-6-258835). This polymer has a feature that the exposed portion is solubilized in a basic aqueous solution because a naphthoquinonediazidosulfonylamide group is changed to a carboxyl group by light irradiation, and is known as a positive photosensitive polyimide precursor. However, at present, such a positive photosensitive polyimide precursor having high sensitivity, excellent pattern shape, and performance for practical use has not been obtained. On the other hand, as a negative type photosensitive polyimide precursor composition, a composition which can obtain a high-resolution pattern and can be developed with a basic aqueous solution has not been actually obtained.

Conventionally, among the above-mentioned photosensitive polyimide precursors, polyamic acid esters having excellent stability have been disclosed in US Pat.
7,512 and US Pat. No. 4,010,83.
As in the method described in the specification 1, an alcohol such as hydroxymethacrylate is reacted with tetracarboxylic dianhydride, and an acid clotting agent such as thionyl chloride is added to the obtained tetracarboxylic diester, A method for producing a polyimide precursor by converting a carboxylic acid into an acid chloride, followed by a reaction with a diamine, and a method disclosed in JP-A-7-568.
As shown in the examples of JP-A No. 8 (1994), esterification is carried out by reacting tetracarboxylic dianhydride with alcohols in the presence of pyridine, and then thionyl chloride is reacted to be converted into an acid chroma intermediate. Thereafter, a method of producing a polyamic acid ester by reacting with a diamine is known.

[0007] However, in the above-mentioned known methods, the esterification reaction takes a long time depending on the kind of tetracarboxylic dianhydride or alcohol, and the esterification reaction does not proceed sufficiently. In particular, this problem is remarkable when a diamine having an acidic group is used as a diamine in order to impart developability with a basic aqueous solution to the polyamic acid ester. When the esterification reaction rate is low, it is difficult to control the molecular weight and the solubility when used as a photosensitive resin composition, and as a result, there is a problem that a pattern having a good shape cannot be obtained.

[0008]

SUMMARY OF THE INVENTION The present invention relates to a polyamic acid ester suitable as a material for a photosensitive resin composition which can be developed with an aqueous liquid, has high resolution and is excellent in pattern shape after development, and a method for producing the same. To provide. Another object of the present invention is to provide a photosensitive resin composition which can be developed with an aqueous liquid, has a high resolution, and has an excellent pattern shape after development.

Another object of the present invention is to provide a method for producing a pattern which is developed with an aqueous liquid and has a high resolution and an excellent pattern shape after development. The present invention also provides an electronic component having excellent reliability, having a polyimide pattern having an excellent shape as a surface protective film, an interlayer insulating film and the like.

[0010]

SUMMARY OF THE INVENTION The present invention relates to (a) a method in which a tetracarboxylic dianhydride and an alcohol having a carbon-carbon unsaturated double bond are converted to a PKb at 25 ° C. (a logarithmic value of a reciprocal of a base dissociation constant in an aqueous solution). ) Is reacted in the presence of a base catalyst of 7 or less to synthesize a dicarboxylic diester, and (b) reacting the dicarboxylic diester with a halogenating agent to convert it into a reactive species; And a diamine containing a diamine having an acidic group.

The present invention also relates to a method for producing a polyamic acid ester, wherein the step (c) comprises reacting a solution of a reactive species by adding a diamine. Further, in the present invention, the amount of the tetracarboxylic acid used in the step (a) is 1 to the amount of the diamine used in the step (c).
The present invention relates to a method for producing a polyamic acid ester in an amount exceeding the equivalent.

Further, the present invention is obtained by the above method,
General formula (I)

Embedded image (Wherein, R ¹ represents a tetravalent organic group, and R ² represents a trivalent or
Indicates the valency of the organic radical, the two R ³ is a monovalent organic group having each independently a monovalent unsaturated carbon-carbon double bond, A is a group showing acidity, n represents 1 or 2 A) a polyamic acid ester having a repeating unit represented by
Further, the present invention relates to the polyamic acid ester having a weight average molecular weight of 25,000 to 60,000.

The present invention further relates to a compound of the general formula (II)

Embedded image (Wherein, R ⁴ represents a tetravalent organic group, two R ⁵ each independently represent a monovalent organic group having a carbon-carbon unsaturated double bond, and R ⁶ , R ⁷ , R ⁸ and R ⁹ independently represent a hydrogen atom or a monovalent organic group, and at least two of these four are monovalent organic groups).

The present invention also relates to a photosensitive resin composition containing a polyamic acid ester as described above or obtained by the above-mentioned production method. The present invention also relates to the above-mentioned photosensitive resin composition further containing a sensitizer or a photopolymerization initiator.

In the present invention, a film formed by using the above photosensitive resin composition is irradiated with light through a mask having a predetermined pattern, and the film is developed using a basic aqueous solution. And a method for producing a pattern. Furthermore, the present invention provides an electronic component having a layer of a pattern obtained by the above-mentioned pattern manufacturing method.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The polyamic acid ester produced by the production method of the present invention is a polyamic acid ester which is suitable as a material for a photosensitive polyimide precursor resin composition and which can be developed using a basic aqueous solution. The method for producing a polyamic acid ester of the present invention comprises the steps of: (a) adding a tetracarboxylic dianhydride and an alcohol having a carbon-carbon unsaturated double bond to PKb at 25 ° C. (a logarithmic value of a reciprocal of a base dissociation constant in an aqueous solution); ) Is reacted in the presence of a base catalyst having 7 or less to synthesize a dicarboxylic acid diester. afterwards,
(B) The dicarboxylic acid diester is reacted with a halogenating agent to convert it into a reactive species, and (c) a reaction between the reactive species and a diamine is performed to obtain a polyamic acid ester.

According to the step (a), the ratio of dicarboxylic acid diester in the reaction product can be 90 mol% or more. Therefore, by using such a reaction product in the next step (b), the efficiency of converting the halogenating agent into a reactive species by reaction is improved, and the yield of the reactive species is also improved. In addition, the molecular weight of the finally obtained polyamic acid ester is improved. At the same time, the esterification rate of the polyamic acid ester can be improved.

The Pkb (logarithm of the reciprocal of the base dissociation constant in an aqueous solution) of the base catalyst used in the step (a) of the present invention means a value at 25 ° C., which is determined depending on the substance. . As a basic catalyst, P at 25 ° C.
Kb is 7 or less, preferably 5 or less, more preferably 3.
3 or less are used. There is no particular lower limit,
Usually, it is 1 or more. A tertiary amine is preferable as the structure of the base catalyst.

As a basic catalyst having a PKb of 3.3 or less,
1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [2.2.2] octane,
Alicyclic amines such as 1,5-diazabicyclo [4.3.0] -5-nonene, and tertiary amines such as triethylamine, tripropylamine, tributylamine and N, N-diisopropylethylamine are preferred. These can be used alone or in combination of two or more. In particular, 1,8-diazabicyclo [5.
4.0] -7-undecene and 1,4-diazabicyclo [2.2.2] octane are preferred. With an amine catalyst having a PKb of more than 7 (for example, pyridine or the like), the esterification reaction of (a) does not sufficiently proceed, so that a polyamic acid ester which finally gives a good photosensitive resin composition cannot be obtained.

The tetracarboxylic dianhydride used in the present invention has excellent heat resistance in electronic parts.
For example, oxydiphthalic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1 , 2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3 5,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, sulfonyl diphthalic dianhydride, m-terphenyl-3,3 ', 4,4 '-Tetracarboxylic dianhydride, p
-Terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, 1,1,1,1,3,3,3-hexafluoro-2,2-bis (2,3- or 3,4 -Dicarboxyphenylpropane dianhydride, 2,2-bis (4 '-(2,3- or 3,4-dicarboxyphenoxy) phenyl) propane dianhydride,
1,1,1,3,3,3-hexafluoro-2,2-bis (4 ′-(2,3- or 3,4-dicarboxyphenoxy) phenyl) propane dianhydride, tetra-siloxane having a siloxane structure Examples thereof include carboxylic dianhydrides, which are used alone or in combination of two or more.

Examples of the alcohol having a carbon-carbon unsaturated double bond include hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl methacrylate. Unsaturated alcohols such as alkyl acrylate or methacrylate, allyl alcohol, vinyl alcohol and the like can be mentioned.

Examples of the diamine having an acidic group include:
3,5-diaminobenzoic acid, 4,4'-dihydroxy-3,
3'-diaminobiphenyl, 44'-diaminodiphenylether-2-carboxylic acid, 4,4'-diamino-3,3 '
-Carboxybiphenylmethane, 4,4'-dihydroxy-3,3'-diaminodiphenyl ether, 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and the like. Used in combination of more than one species.

Other diamines which can be used in combination with the above-mentioned diamines include 2,2'-dialkyl-4,4'-diaminobenzidine, 2,2 ', 6,6'-tetraalkyl-4,
Those having a benzidine structure such as 4′-diaminobenzidine (the alkyl group is a methyl group, an ethyl group or an isopropyl group) are preferable, and 4,4 ′-(or 3,4′-, , 3 '-, 2,4'-,
2,2 ′-) diaminodiphenyl ether, 4,4 ′-(or 3,4′-, 3,3′-, 2,4′-, 2,2 ′-) diaminodiphenylmethane, 4,4 ′-(or 3,4 '-, 3,3'
-, 2,4 '-, 2,2'-) diaminodiphenylsulfone, 4,4'- (or 3,4 '-, 3,3'-, 2,4 '-, 2,2'-) diamino Diphenyl sulfide, paraphenylenediamine, metaphenylenediamine, p-xylenediamine, m-xylenediamine, o-tolidine, o-tolidine sulfone,
4,4′-methylene-bis- (2,6-diethylaniline), 4,4′-methylene-bis- (2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-
Diaminonaphthalene, 4,4'-benzophenonediamine, bis- {4- (4'-aminophenoxy) phenyl} sulfone, 1,1,1,3,3,3-hexafluoro-
2,2-bis (4-aminophenyl) propane, 2,2-
Bis {4- (4'-aminophenoxy) phenyl} propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-5,5'-tetramethyl-4,4'-diaminodiphenylmethane , Bis {4- (3'-aminophenoxy) phenyl} sulfone, 2,2-bis (4-aminophenyl) propane and the like can also be used in combination. These are used alone or in combination of two or more.
In addition, a diamine having a siloxane structure can be used in combination for improving the adhesiveness.

As the organic solvent used in the step (a) of the present invention, an amide-based solvent is preferable because of good production of reactive species, and an aprotic polar solvent is more preferable in view of the solubility and reactivity of the raw materials. , N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N-methyl-2-
The use of pyridone is particularly preferred. These can be used alone or 2
It can be used in combination of more than one species.

The reaction between the tetracarboxylic dianhydride and the alcohol adversely affects the reaction with the halogenating agent in the next step if excess alcohol remains in the system.
The alcohol is preferably used in an amount of preferably 2 to 3 mol, more preferably 2 to 2.3 mol, per 1 mol of the tetracarboxylic dianhydride.

The amount of the base catalyst used in the reaction is usually from 0.01 to 0. 1 mol per mol of tetracarboxylic anhydride.
5 mol is preferable, and 0.01 to 0.1 mol is more preferable. If the amount of the catalyst used does not adversely affect the conversion of the esterification reaction, the remaining amount of the catalyst is reduced.

The reaction temperature of the esterification reaction is not particularly limited, and is usually 20 to 1 depending on the reaction rate of the esterification reaction.
It is preferable to carry out in the range of 00 ° C. The amount of the reaction solvent used is not particularly limited, and is usually preferably about 2 to 10 times the weight of the tetracarboxylic anhydride.

In the present invention, as step (b), a halogenating agent is added directly to the reaction solution of the ester compound synthesized by the above-mentioned method to convert it into a reactive species. Thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride, and the like used in the acid chloride reaction of carboxylic acids can be used. Of these, the use of thionyl chloride is preferred.

The amount of the halogenating agent to be used is preferably 1.8 to 3 mol, more preferably 2.0 to 2.5 mol, based on tetracarboxylic dianhydride. The reaction temperature is
-10 to + 30 ° C is preferred. A diamine is reacted with the reactive species obtained by the above-mentioned method as step (c) to synthesize a polyamic acid ester. At this time, the amount of the diamine used relative to the tetracarboxylic dianhydride is 0.7 to
It is preferable to use 1.3 equivalents. Further, from the viewpoint of the transparency of the polymer, the amount of the tetracarboxylic dianhydride used is preferably more than 1 equivalent to the amount of the diamine. Therefore, the amount of the diamine used relative to the tetracarboxylic dianhydride is preferably 0.7 equivalent or more and less than 1 equivalent.

The reaction temperature ranges from 0 to 10 due to the problem of the reaction rate.
0 ° C is preferred, and 10 to 80 ° C is more preferred. The reaction time is preferably 1 to 24 hours. The method of reacting the reactive species with the diamine may be either a method of directly adding a diamine or a solution of the diamine to the reactive species solution, or a method of adding the reactive species solution to the diamine solution. From the viewpoint of reproducibility, a method of directly adding a diamine or a solution of a diamine to a reactive species solution is preferable.

As the solvent for dissolving the diamine, the same solvent as that used for the reactive species solution may be used.
Other solvents that are inert to the reactive species and dissolve the diamines can also be used. Specific examples of such a solvent include solvents such as N, N-dimethylformamide, dimethylsulfoxide, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and the like.

The reaction between the reactive species and the diamine can be accelerated by using a tertiary amine which functions as a dehydrochlorinating agent. Specific examples of the tertiary amine that can be used include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, and 3,5-dimethylpyridine. , N, N-dimethylaminopyridine, triethylamine, tripropylamine, tributylamine and the like. These can be used alone or in combination of two or more. Particularly, pyridine is preferable. The use amount of the tertiary amine is preferably from 2 to 5 equivalents to the use amount of the halogenating agent. The polyamide acid ester of the present invention can be produced by the above production method.

The polyamic acid ester of the present invention thus obtained has a repeating unit represented by the general formula (I). The repeating unit represented by the general formula (I) has an acidic group represented by A, and the repeating unit can form a resin film soluble in a basic aqueous solution.

R ¹ in the general formula (I) is preferably a residue of a tetracarboxylic dianhydride or a derivative thereof capable of forming a polyamic acid ester by reacting with a diamine, and is obtained by curing. From the viewpoint of the mechanical properties, heat resistance and adhesiveness of the polyimide film, 4
It is preferably a valent organic group. Among the tetravalent organic groups having 4 or more carbon atoms, organic groups having a total carbon number of 6 to 30 including an aromatic ring (benzene ring, naphthalene ring, etc.) are more preferable. In the polyamic acid ester molecule, in the plurality of repeating units, all R ^{1 s} may be the same or different.

In the general formula (I), the acidic group A is not particularly limited, but may be a sulfonic group (—SO ₃
H), a sulfinic acid group (—SO ₂ H), a carboxyl group (—COOH) and a phenolic hydroxyl group are preferable because they exhibit good solubility. Among these,
A carboxyl group and a phenolic hydroxyl group are particularly preferable because the synthesis of the polyimide precursor is easy.

In the general formula (I), a diamine residue R ² to which an acidic group A is bonded is a diamine residue capable of forming a polyamic acid ester by reacting with a tetracarboxylic acid or a derivative thereof. Is preferably
From the viewpoint of the mechanical properties, heat resistance and adhesiveness of the polyimide film obtained by curing, it is preferably a trivalent or tetravalent organic group having an aromatic ring and having 6 to 30 carbon atoms in total. In addition,
All R ² in the polyamic acid ester molecule may be the same or different.

Two R ³ in the general formula (I) are a monovalent organic group having a carbon-carbon unsaturated double bond, and two R ³ in each repeating unit may be the same or different. In addition, all R ^{3 's} may be the same or different in a plurality of repeating units of the general formula (I) in the polyamic acid ester molecule. Examples of the monovalent organic group having a carbon-carbon unsaturated double bond represented by R ³ include a vinyl group, an allyl group, a methacryloyloxyalkyl group, an acryloyloxyalkyl group, and a vinyl ether group.

Embedded image (However, R ¹⁰ , R ¹¹ and R ¹² are each independently selected from hydrogen, an alkyl group, a phenyl group, a vinyl group and a propenyl group, and R ¹³ represents a divalent organic group) The organic group to be used is preferable because it can impart high-sensitivity photosensitivity. The alkyl group has 1 to 1 carbon atoms.
Four are preferred. The divalent organic group represented by R ^13, a methylene group, an ethylene group, an alkylene group having 1 to 4 carbon atoms such as a propylene group are preferable. Among them, particularly, methacryloyloxyalkyl groups and acryloyloxyalkyl groups (where the alkyl has 1 carbon atom)
To 4) are suitable for the present invention because they not only realize high sensitivity, but also are easy to synthesize.

The polyamic acid ester of the present invention preferably further has a repeating unit represented by the general formula (II). The repeating unit represented by the general formula (II) has a biphenylene group having a substituent at a specific position, and by having this with the repeating unit represented by the general formula (I), a basic aqueous solution can be obtained. A polyimide precursor which gives a photosensitive polyimide precursor composition which is excellent in pattern shape, resolution, sensitivity and the like and has a short development time without impairing the solubility of the polyimide.

[0039] In the repeating unit represented by formula (II), the description of ^{R 5} is the same as ^{R 3} in the general formula (I). In the repeating unit represented by the general formula (II), R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom or a monovalent organic group, and at least two of these four are monovalent. Is an organic group. In particular, those having a monovalent organic group in each of two aromatic rings are preferable. As the monovalent organic group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group and a propyl group, a halogen, a halogenated alkyl group and the like are preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. . Among these, those in which R ⁶ and R ⁷ are methyl groups, or those in which all of R ⁶ , R ^7, R ⁸ and R ⁹ are methyl groups are particularly preferred because resolution is improved.

The polyamic acid ester of the present invention may contain other repeating units. This repeating unit has the following general formula (III)

Embedded image (Wherein, R ¹⁴ is a tetravalent organic group, R ¹⁵ is a divalent organic group, and two R ¹⁶ are each independently a monovalent organic group or a hydrogen atom, and each of the general formulas (I) and ( Excluding the repeating unit represented by II)).

Specific examples of the tetravalent organic group represented by R ¹⁴ include those similar to the organic groups represented by R ¹ , and preferred ones are also the same. Specific examples of the monovalent organic group represented by R ¹⁶ include those represented by R ³ , and a polyamic acid ester molecule having no carbon-carbon unsaturated double bond, a methyl group, an ethyl group, It may partially have an alkyl group such as n-propyl group, isopropyl group and n-butyl group, an aryl group such as phenyl group, and a hydrocarbon group such as aralkyl group such as benzyl group. Also, R ³ , R ⁵ and R in the polyamic acid ester molecule
^{As 16} , it may have a hydrogen atom in part.

R ¹⁵ is a divalent organic group, and preferably contains an aromatic ring or silicon from the viewpoints of mechanical properties, heat resistance, adhesiveness and the like of the polyimide film obtained by curing, and preferably contains an aromatic ring. And those having 6 to 30 carbon atoms are preferable, and in the case of containing silicon, those having a (poly) siloxane bond having 1 to 10 silicon atoms are preferable. When a plurality of repeating units represented by the general formula (III) are present in a molecule, a plurality of R ¹⁵ may be the same or different.

In the polyamic acid ester of the present invention,
The proportion of the repeating units represented by the general formulas (I), (II) and (III) is 5 to 100 mol% and (II) is 95 to 0 mol% in terms of mol percentage of each repeating unit. , (III) is preferably 0 to 50 mol% because of excellent balance between developability in a basic aqueous solution and a good pattern shape, and (I) is preferably 20 to 90 mol%.
(II) is more preferably 70 to 5 mol%, and (III) is more preferably 0 to 30 mol%. From the viewpoint of the balance between resolution and developability, (I) is 20 to 90 mol% and (II) is preferably 7
More preferably, 0 to 5 mol% and (III) are 5 to 30 mol%.

In the present invention, 95 mol% or more of the esterification rate of the polyamic acid ester, that is, the total of the groups represented by R ³ , R ⁵ and R ¹⁶ which are the side chains of the polyamic acid ester is esterified. Is preferred. If it is less than 95 mol%, good resolution, pattern shape and residual film ratio cannot be obtained. The esterification rate can be calculated from, for example, NMR.

The molecular weight of the polyamic acid ester in the present invention is preferably from 10,000 to 200,000, more preferably from 25,000 to 60,000 in terms of weight average molecular weight from the viewpoint of developability and film quality. The weight average molecular weight can be measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.

Next, the photosensitive resin composition of the present invention will be described. The photosensitive resin composition of the present invention is used as a negative photosensitive material that cures an exposed portion. The photosensitive resin composition of the present invention preferably contains a sensitizer or a photopolymerization initiator in order to achieve a practically usable photosensitive sensitivity. Preferred examples of the sensitizer include Michler's ketone, bis-4,4'-diethylaminobenzophenone, benzophenone, 3,5-bis (diethylaminobenzylidene)
-N-methyl-4-piperidone, 3,5-bis (dimethylaminobenzylidene) -N-methyl-4-piperidone, 3,5-bis (diethylaminobenzylidene) -N
-Ethyl-4-piperidone, 3,3'-carbonylbis (7-diethylamino) coumarin, riboflavin tetrabutyrate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one , 2,
4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone,
3,5-dimethylthioxanthone, 3,5-diisopropylthioxanthone, 1-phenyl-2- (ethoxycarbonyl) oxyiminopropan-1-one, benzoin ether, benzoin isopropyl ether, benzanthrone, 5-nitroacenaphthene, 2-nitroacenaphthene Nitrofluorene, anthrone, 1,2-benzanthraquinone,
1-phenyl-5-mercapto-1H-tetrazole,
Thioxanthen-9-one, 10-thioxanthenone,
3-acetylindole, 2,6-di (p-dimethylaminobenzal) -4-carboxycyclohexanone,
2,6-di (p-dimethylaminobenzal) -4-hydroxycyclohexanone, 2,6-di (p-diethylaminobenzal) -4-carboxycyclohexanone,
2,6-di (p-diethylaminobenzal) -4-hydroxycyclohexanone, 4,6-dimethyl-7-ethylaminocoumarin, 7-diethylamino-4-methylcoumarin, 7-diethylamino-3- (1-methylbenzimidazolyl ) Coumarin, 3- (2-benzimidazolyl) -7-diethylaminocoumarin, 3- (2-benzothiazolyl) -7-diethylaminocoumarin, 2- (p
-Dimethylaminostyryl) benzoxazole, 2-
(P-dimethylaminostyryl) quinoline, 4- (p-
Dimethylaminostyryl) quinoline, 2- (p-dimethylaminostyryl) benzothiazole, 2- (p-dimethylaminostyryl) -3,3-dimethyl-3H-indole and the like. These are used alone or in combination of two or more.

The sensitizer is preferably used in an amount of 0.1 to 50 parts by weight, more preferably 0.3 to 20 parts by weight, based on 100 parts by weight of the polyamic acid ester. If the amount is out of the range of 0.1 to 50 parts by weight, the sensitizing effect cannot be obtained or the developing property tends to be adversely affected. As the sensitizer, one kind of compound may be used, or a mixture of several kinds may be used.

As the photopolymerization initiator, for example, 4
-Diethylaminoethyl benzoate, 4-dimethylaminoethyl benzoate, 4-diethylaminopropyl benzoate, 4-dimethylaminopropyl benzoate, 4-dimethylaminoisoamyl benzoate, N-
Phenylglycine, N-methyl-N-phenylglycine, N- (4-cyanophenyl) glycine, 4-dimethylaminobenzonitrile, ethylene glycol dithioglycolate, ethylene glycol di (3-mercaptopropionate), trimethylolpropane Thioglycolate, trimethylolpropane tri (3-mercaptopropionate), pentaerythritol tetrathioglycolate, pentaerythritol tetra (3-mercaptopropionate), trimethylolethanetrithioglycolate, trimethylolpropanetrithioglycol Rate, trimethylolethanetri (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), thioglycolic acid, α-mercaptopropion , T- butyl peroxybenzoate, t- butyl peroxy-methoxybenzoate, t
-Butylperoxynitrobenzoate, t-butylperoxyethylbenzoate, phenylisopropylperoxybenzoate, di-tert-butyldiperoxyisophthalate, tri-tert-butyltriperoxytrimellitate, tri-tert-butyltriperoxytrimesitate,
Tetra-t-butyltetraperoxypyromellitate,
2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ′,
4,4'-tetra (t-amylperoxycarbonyl)
Benzophenone, 3,3 ′, 4,4′-tetra (t-hexylperoxycarbonyl) benzophenone, 2,6-
Di (p-azidobenzal) -4-hydroxycyclohexanone, 2,6-di (p-azidobenzal) -4-carboxycyclohexanone, 2,6-di (p-azidobenzal) -4-methoxycyclohexanone, 2,6-di ( p-azidobenzal) -4-hydroxymethylcyclohexanone, 3,5-di (p-azidobenzal) -1-methyl-4-piperidone, 3,5-di (p-azidobenzal) -4-piperidone, 3,5-di ( p-azidobenzal) -N-acetyl-4-piperidone, 3,5-di (p
-Azidobenzal) -N-methoxycarbonyl-4-piperidone, 2,6-di (p-azidobenzal) -4-hydroxycyclohexanone, 2,6-di (m-azidobenzal) -4-carboxycyclohexanone, 2,6-
Di (m-azidobenzal) -4-methoxycyclohexanone, 2,6-di (m-azidobenzal) -4-hydroxymethylcyclohexanone, 3,5-di (m-azidobenzal) -N-methyl-4-piperidone, 3, 5-di (m-azidobenzal) -4-piperidone, 3,5-di (m-azidobenzal) -N-acetyl-4-piperidone, 3,5-di (m-azidobenzal) -N-methoxycarbonyl-4- Piperidone, 2,6-di (p-azidocinnamylidene) -4-hydroxycyclohexanone,
2,6-di (p-azidocinnamylidene) -4-carboxycyclohexanone, 2,6-di (p-azidocinnamylidene) -4-hydroxymethylcyclohexanone,
3,5-di (p-azidocinnamylidene) -N-methyl-4-piperidone, 4,4′-diazidochalcone,
3′-diazidochalcone, 3,4′-diazidochalcone, 4,3′-diazidochalcone, 1,3-diphenyl-1,2,3-propanetrione-2- (o-acetyl) oxime, 1 , 3-Diphenyl-1,2,3-propanetrione-2- (on-propylcarbonyl) oxime, 1,3-diphenyl-1,2,3-propanetrione-2- (o-methoxycarbonyl) oxime ,
1,3-diphenyl-1,2,3-propanetrione-
2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-1,2,3-propanetrione-2- (o-
Benzoyl) oxime, 1,3-diphenyl-1,2,2
3-propanetrione-2- (o-phenyloxycarbonyl) oxime, 1,3-bis (p-methylphenyl) -1,2,3-propanetrione-2- (o-benzoyl) oxime, 1,3- Bis (p-methoxyphenyl) -1,2,3-propanetrione-2- (o-ethoxycarbonyl) oxime, 1- (p-methoxyphenyl) -3- (p-nitrophenyl) -1,2,3 -Propanetrione-2- (o-phenyloxycarbonyl)
Oximes and the like can be used, but are not limited thereto.

The photopolymerization initiator is preferably used in an amount of 0.1 to 50 parts by weight, more preferably 0.3 to 20 parts by weight, based on 100 parts by weight of the polyamic acid ester of the present invention. If the amount is out of the range of 0.1 to 50 parts by weight, the desired sensitizing effect cannot be obtained or the developability tends to be adversely affected. One type of compound may be used as the photopolymerization auxiliary material, or several types may be mixed.

The photosensitive resin composition of the present invention may further contain a copolymer monomer in addition to the above-mentioned sensitizer or photopolymerization initiator in order to achieve a practically usable photosensitive sensitivity. The copolymerization monomer is a compound having a carbon-carbon double bond, and can facilitate photopolymerization. As copolymerized monomers, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate,
Ethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolpropane tetraacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl Glycol dimethacrylate, ethylene glycol dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexamethacrylate, tetramethylolpropane tetramethacrylate, tetraethylene glycol dimethacrylate, etc. are preferred, but these are preferred. Not a constant.

These copolymer monomers are preferably blended in an amount of 1 to 100 parts by weight, more preferably 3 to 50 parts by weight, based on 100 parts by weight of the polyimide precursor of the present invention. If the amount is outside the range of 1 to 100 parts by weight, the desired effect tends to decrease, and the developing effect tends to be adversely affected. In addition, as a copolymerization monomer, one kind of compound may be used, or a plurality of kinds may be mixed and used.

[0052] The photosensitive resin composition of the present invention may contain a suitable organic solvent. If it is dissolved in an appropriate organic solvent, it can be used in a solution (varnish) state, which is convenient when forming a film. As the solvent used in this case, an aprotic localized solvent is desirable from the viewpoint of solubility, and specifically, N-methyl-2-pyrrolidone, N-
Acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide, N-acetyl-ε-caprolactam, dimethylimidazolidinone, Preferred examples include diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and γ-butyrolactone. These may be used alone or as a mixed system. The organic solvent may be a solvent in which the solvent used in the synthesis reaction of the polyimide precursor is left as it is, or may be a newly added solvent to the isolated polyimide precursor. Further, in order to improve the coatability, a solvent such as toluene, xylene, diethyl ketone, or methoxybenzene may be mixed within a range that does not adversely affect the solubility of the polymer. Although the amount of the organic solvent is not particularly limited, it is generally preferable to use 100 to 200 parts by weight based on 100 parts by weight of the polyimide precursor.

The pattern manufacturing method of the present invention uses the photosensitive resin composition of the present invention obtained as described above to form a polyimide film composed of a cured product of the composition by a photolithography technique. is there. In the pattern manufacturing method of the present invention, first, a film made of the photosensitive resin composition of the present invention is formed on the surface of a supporting substrate. Here, in order to improve the adhesiveness between the coating or the polyimide coating after heat curing and the supporting substrate, the surface of the supporting substrate may be previously treated with an adhesion aid.

The coating made of the photosensitive resin composition can be formed, for example, by forming a varnish film of the photosensitive resin composition and then drying it. The varnish film can be formed by a means appropriately selected from means such as spin coating using a spinner, dipping, spray printing, and screen printing, depending on the viscosity of the varnish. The thickness of the film can be adjusted by the application conditions and the solid content concentration of the present composition. Further, the film formed on the support in advance is peeled from the support to form a sheet made of the photosensitive resin composition, and the sheet is adhered to the surface of the air-supporting substrate, whereby the above-described film is formed. It may be formed.

Next, the film is irradiated with light (usually using ultraviolet light) through a photomask having a predetermined pattern. This exposure step can be performed using a contact / proximity exposure machine using an ultra-high pressure mercury lamp, a mirror projection exposure machine, a g-ray stepper, an i-ray stepper, other ultraviolet rays, a visible light source, X-rays, an electron beam and the like. . In particular, the photosensitive resin composition of the present invention has excellent light transmittance with respect to i-line, and thus is suitable for use in an i-line exposure machine such as an i-line stepper.

Next, the unexposed portion is dissolved and removed with a basic aqueous solution to obtain a desired relief pattern. This developing step can be performed using a normal photoresist developing device or the like. In the pattern manufacturing method of the present invention, a basic aqueous solution is used as a developer. The developer may be an aqueous solution of one compound or an aqueous solution of two or more compounds as long as the aqueous solution exhibits basicity. The basic aqueous solution is usually a solution in which a basic compound is dissolved in water.
The concentration of the basic compound is usually from 0.1 to 50% by weight, preferably from the influence on a supporting substrate and the like.
More preferably, it is 0% by weight. The developer is
In order to improve the solubility of the polyimide precursor, further contains an aqueous solution such as methanol, ethanol, propanol, isopropyl alcohol, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide. Is also good.

The basic compound includes, for example, hydroxides or carbonates of alkali metals, alkaline earth metals or ammonium ions, amine compounds and the like. Specifically, 2-dimethylaminoethanol, 3
-Dimethylamino-1-propanol, 4-dimethylamino-1-butanol, 5-dimethylamino-1-pentanol, 6-dimethylamino-1-hexanol, 2
-Dimethylamino-2-methyl-1-propanol, 3
-Dimethylamino-2,2-dimethyl-1-propano-
2-diethylaminoethanol, 3-diethylamino-1-propanol, 2-diisopropylaminoethanol, 2-di-n-butylaminoethanol, N, N
-Dibenzyl-2-aminoethanol, 2- (2-dimethylaminoethoxy) ethanol, 2- (2-diethylaminoethoxy) ethanol, 1-dimethylamino-2
-Propanol, 1-diethylamino-2-propano-
, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N
-T-butyldiethanolamine, N-lauryldiethanolamine, 3-diethylamino-1,2-propanediol, triethanolamine, triisopropanolamine, N-methylethanolamine, N-ethylethanolamine, Nn-butylethanolamine, N
-T-butylethanolamine, diethanolamine,
Diisopropanolamine, 2-aminoethanol, 3
-Amino-1-propanol, 4-amino-1-butanol, 6-amino-1-hexanol, 1-amino-2
-Propanol, 2-amino-2,2-dimethyl-1-
Propanol, 1-aminobutanol, 2-amino-1
-Butanol, N- (2-aminoethyl) ethanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 3-amino-1, 2-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate , Ammonium hydrogen carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, aminomethanol, 2-
Aminoethanol, 3-aminopropanol, 2-aminopropanol, methylamine, ethylamine, propylamine, isopropylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, trimethylamine, triethylamine, tripropylamine, triisopropylamine It is preferable to use other compounds as long as they are soluble in water and the aqueous solution exhibits basicity.

The relief pattern formed by development is then washed with a rinsing liquid to remove the developing solvent. Preferable examples of the rinsing liquid include methanol, ethanol, isopropyl alcohol, water, and the like having good miscibility with the developing liquid. By heating the relief pattern obtained by the above-described process at a temperature selected from the range of 150 ° C. to 450 ° C., a resin pattern made of polyimide can be obtained with high resolution. Since this resin pattern has high heat resistance and excellent mechanical properties,
It is used as a surface protective film of a semiconductor element, an interlayer insulating film of a thin-film multilayer wiring board, and the like.

The photosensitive resin composition of the present invention can be used for electronic parts such as semiconductor devices and multilayer wiring boards, and more specifically, for surface protection films and interlayer insulating films of semiconductor devices and multilayer wiring boards. It can be used for forming an interlayer insulating film and the like. The electronic component of the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed using the composition, and can have various structures.

An example of the manufacturing process of the semiconductor device will be described below. FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure. In the figure, a semiconductor substrate such as a Si substrate having a circuit element is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and a first conductor layer is formed on the exposed circuit element. . A film 4 of a polyimide resin or the like as an interlayer insulating film is formed on the semiconductor substrate by a spin coating method or the like (step (a)).

Next, a photosensitive resin layer 5 of a chlorinated rubber type or a phenol novolak type is formed on the interlayer insulating film 4 by spin coating, and a predetermined portion of the interlayer insulating film 4 is exposed by a known photolithography technique. Window 6A is provided as described above (step (b)). The interlayer insulating film 4 in the window 6A is selectively etched by a dry etching means using a gas such as oxygen or carbon tetrafluoride, and a window 6B is opened. Next, the photosensitive resin layer 5 is completely removed by using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B (step (c)).

Further, using a known photolithography technique,
The conductor layer 7 is formed, and the electrical connection with the first conductor layer 3 is made completely (step (d)). When a multilayer wiring structure of three or more layers is formed, the above steps are repeated to form each layer.

Next, a surface protection film 8 is formed. In the example of this figure, the surface protective film is coated with the photosensitive polymer composition by a spin coating method, dried, irradiated with light from a mask on which a pattern for forming a window 6C is formed on a predetermined portion, and then exposed to a base. A pattern is formed by developing with an aqueous solution, and heated to form a polyimide film. This polyimide film protects the conductor layer from external stress, α-rays and the like, and the resulting semiconductor device has excellent reliability. In the above example, the interlayer insulating film can be formed using the photosensitive resin composition of the present invention.

[0064]

The present invention will be described below with reference to examples. (Example 1) A. Synthesis of polyamic acid ester In a 200 ml four-necked flask, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) 17.6 was prepared.
5 g (60 mmol), 2-hydroxyethyl methacrylate (HEMA) 15.62 g (120 mmol),
0.27 g (1.8 mmol) of 1,8-diazabicyclo (5.4.0) -7-undecane (DBU), 0.04 g of hydroquinone, N, N'-dimethylacetamide (DMA
c) 80 g was added and stirred at 60 ° C., which turned into a transparent liquid in 1 hour. At this time, the ratio of the dicarboxylic acid diester in the reaction product was 96.3 mol% (analyzed by reverse phase chromatography). After the solution was stirred at room temperature for 10 hours, the flask was cooled with ice and 15.70 g (132 mmol) of thionyl chloride was added dropwise over 20 minutes. Thereafter, the mixture was stirred at room temperature for 2 hours to obtain a solution containing acid chloride.

The flask was cooled with ice and 7.40 g (48.6 mmol) of 3,5-diaminobenzoic acid (DABA), 2,2'-dimethylbenzidine (DMAP) 1.1.
5 g (5.4 mmol), pyridine 10.441 g (13
2 mmol), 0.04 g of hydroquinone and 80 g of N, N'-dimethylacetamide (DMAc) at 10 ° C.
The solution was dropped in one hour while maintaining the following. Then at room temperature
The mixture was stirred for 0 minute, poured into 2 liters of water, the precipitated polymer was collected by filtration, washed twice with water, and dried under vacuum. The weight average molecular weight of this polyamic acid ester was determined by GPC (gel
Permeation chromatography) was 30,000 in terms of polystyrene. The esterification ratio was 97.6%.

When the obtained solution of the polyamic acid ester was dried, an infrared absorption spectrum (JIR-100, manufactured by JEOL Ltd.) was measured by the KBr method. absorption of C = O of amide group near ^-1, the absorption of N-H were observed at around 3300 cm ^-1.

B. Preparation of Photosensitive Resin Composition 10 g of the obtained polymer was dissolved in 15 g of γ-butyrolactone, and 100 mg of Michler's ketone and 1,3-diphenyl-1,2,3-propanetrione-2- (o- After adding and dissolving 200 mg of (ethoxycarbonyl) oxime and 2.0 g of ethylene glycol diacrylate, the solution was filtered under pressure using a filter having a pore size of 5 μm to obtain a photosensitive resin composition in the form of a solution.

C. Evaluation of Photosensitive Resin Composition The obtained composition was spin-coated on a silicon wafer with a spinner, and then dried on a hot plate at 90 ° C. for 3 minutes to obtain a coating having a thickness of 15 μm. The coating film was exposed through a photomask using an i-line stepper. After the exposure, the film was developed by immersing it in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (developer) at 20 ° C. for 1 minute, and then rinsed with water. As a result, a sharp 10 μm
An m-width relief pattern was obtained. The residual film ratio after development with respect to the film thickness after coating and drying was as good as 95%.

(Examples 2 to 6 and Comparative Example 1) Polyamic acid esters and polycarboxylic acid esters were prepared in the same manner as in Example 1 except that the base, tetracarboxylic dianhydride, alcohol and diamine shown in Table 1 were used. The photosensitive resin composition was prepared and evaluated.

[0070]

[Table 1]

Note) In the table, ODPA is oxydiphthalic anhydride, HAB is 3,3'-diamino-4,4'-dihydroxybiphenyl, MeOH is methanol, and TMAP is 2,2 '.
-6,6'-tetramethylbenzidine, DDE is 4,4'-
Diaminodiphenyl ether, Py means pyridine.

The development time was 20 minutes with a developer consisting of a 2.38% by weight aqueous solution of tetraammonium hydroxide.
Those which can be developed in 0 seconds or less were evaluated as good. The amount of the base used in the synthesis was represented by mol% based on the acid dianhydride. The residual film ratio is (film thickness after development) / (film thickness after coating and drying) × 10
0 was calculated. The resolution was represented by a minimum pattern having a well-formed opening after development. In addition, the shape having no development residue and a rectangular cross section of the pattern was regarded as good.

[0073]

According to the method for producing a polyamic acid ester of the present invention, a polyamic acid ester suitable for a photosensitive resin composition which can be developed with an aqueous liquid, has high resolution and is excellent in pattern shape after development is obtained. can get. Further, the photosensitive resin composition of the present invention can be developed with an aqueous liquid, has high resolution and is excellent in pattern shape after development.

According to the method for producing a pattern of the present invention,
By developing with an aqueous solution, a pattern having high resolution and excellent pattern shape after development can be obtained. The electronic component of the present invention has a polyimide pattern having an excellent shape as a surface protective film, an interlayer insulating film, and the like, and has excellent reliability.

[Brief description of the drawings]

FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1: Semiconductor substrate, 2: Protective film, 3: 1st conductor layer,
4 ... interlayer insulating film layer, 5 ... photosensitive resin layer, 6A, 6B,
6C: window, 7: second conductor layer, 8: surface protective film layer.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Junko Imai 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside the Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. (72) Inventor Makoto Kaji 4--13, Higashimachi, Hitachi City, Ibaraki Prefecture No. 1 F term in Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. (Reference) 2H025 AA02 AA03 AB15 AB16 AB17 AC01 AD01 BC43 BC69 BC92 BJ10 CA00 FA03 FA17 FA29 4J043 PA02 PA04 PA19 QB15 QB23 QB31 RA35 SA06 SA54 SA62 SA71 SA81 SA82 SB01 SB02 SB03 SB03 TA26 TA32. 5F058 AA10 AC02 AC07 AF04 AG01 AH01 AH02 AH03

Claims (10)

[Claims] (A) A tetracarboxylic dianhydride and an alcohol having a carbon-carbon unsaturated double bond have a PKb (a logarithm of a reciprocal of a base dissociation constant in an aqueous solution) of 7 at 25 ° C.
Reacting in the presence of the following base catalyst to synthesize a dicarboxylic acid diester, and (b) reacting the dicarboxylic acid diester with a halogenating agent to convert it into a reactive species;
A method for producing a polyamic acid ester, comprising reacting the reactive species with a diamine containing a diamine having an acidic group. 2. The method for producing a polyamic acid ester according to claim 1, wherein in the step (c), a diamine is added to the solution of the reactive species to cause a reaction. 3. The polyamide acid ester according to claim 1, wherein the amount of the tetracarboxylic acid used in the step (a) is more than 1 equivalent to the amount of the diamine used in the step (c). Manufacturing method. 4. A compound of the general formula (I) obtained by the method according to claim 1, 2 or 3. (Wherein, R ¹ represents a tetravalent organic group, and R ² represents a trivalent or
Indicates the valency of the organic radical, the two R ³ is a monovalent organic group having each independently a monovalent unsaturated carbon-carbon double bond, A is a group showing acidity, n represents 1 or 2 A) a polyamic acid ester having a repeating unit represented by the formula: 5. The polyamide acid ester according to claim 4, wherein the weight average molecular weight is 25,000 to 60,000. 6. A compound of the general formula (II) (Wherein, R ⁴ represents a tetravalent organic group, two R ⁵ each independently represent a monovalent organic group having a carbon-carbon unsaturated double bond, and R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom or a monovalent organic group, and at least two of these four groups represent a monovalent organic group). Polyamic acid esters. 7. A photosensitive resin composition comprising the polyamic acid ester according to claim 4, 5 or 6. 8. The photosensitive resin composition according to claim 7, further comprising a sensitizer or a photopolymerization initiator. 9. A film formed by using the photosensitive resin composition according to claim 8 is irradiated with light through a mask having a predetermined pattern, and then the film is developed using a basic aqueous solution. A pattern manufacturing method characterized by the above-mentioned. 10. An electronic component having a pattern layer obtained by the pattern manufacturing method according to claim 9.