JPH11174679A - Positive photosensitive resin composition and manufacture of relief pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition extremely high in sensitivity to active light such as i-line and capable of forming a satisfactory pattern by using an alkaline water solution, and a manufacturing method enabling a satisfactory relief pattern to be formed by exposure of active light such as i-line and by development using the alkaline developer. SOLUTION: In a positive photosensitive resin composition including (A) a polyimide precursor having a carboxyl radical or a phenolic hydroxyl radical, and (B) a compound producing an acid by light, the (A) constituent is a mixture of two kinds of polyimide precursors a ratio of whose dissolving speeds is 5 or more in an alkaline water solution, and, in a manufacturing method for a relief pattern, this positive photosensitive resin composition is spread over a substrate, dried, thereafter irradiated with active light, developed by the alkaline water solution, and heated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a positive photosensitive resin composition and a relief pattern, and more particularly, it can be applied as a surface protective film or an interlayer insulating film of an electronic component such as a semiconductor device by heat treatment. The present invention relates to a positive-type photosensitive resin composition which becomes a polyimide-based heat-resistant polymer and a method for producing a relief pattern using the composition.

[0002]

2. Description of the Related Art Polyimide has excellent heat resistance and mechanical properties.
Further, it is widely used as a surface protective film and an interlayer insulating film of a semiconductor element because of its advantages such as easy film formation and flattening of the surface. When polyimide is used as a surface protective film and an interlayer insulating film, the process of forming through holes and the like is performed mainly by an etching process using a positive photoresist. However, there is a problem that the process involves coating and peeling of a photoresist, which is complicated. Accordingly, heat-resistant materials having both photosensitivity have been studied for the purpose of streamlining work steps.

With respect to the photosensitive polyimide composition, a polyimide precursor composition having a photosensitive group introduced through an ester bond (Japanese Patent Publication No. 52-30207, etc.), a carbon-carbon which can be dimerized or polymerized with a polyamic acid by actinic radiation. A composition containing a compound containing a double bond and an amino group and an aromatic bisazide (Japanese Patent Publication No. 3-36861, etc.) is known. When the photosensitive polyimide precursor composition is used, it is usually applied in a solution state on a substrate, dried, irradiated with an actinic ray through a mask, and developed to form a pattern.

However, the photosensitive polyimide composition requires the use of an organic solvent in a developer. Since the amount of the developer used is several times the amount of the photosensitive polyimide precursor composition used, there is a problem that a large load is imposed on the environment when processing the waste developer. Therefore, a photosensitive polyimide composition which can be developed with an aqueous developer which can easily treat a waste developer has been desired in recent years, particularly in consideration of the environment. Further, since the photosensitive polyimide composition is a negative type, when switching from an etching process using a positive type photoresist to a negative type photosensitive polyimide precursor, it is necessary to change a mask used in an exposure step. There is a problem.

The positive photosensitive polyimide precursor composition includes a polyimide precursor having an o-nitrobenzyl group introduced through an ester bond (JP-A-60-37550), a polyamide acid ester containing a carboxyl group and o-nitrobenzyl group.
-A composition containing a quinonediazide compound (JP-A-4-16
No. 8441), a composition containing a polyamic acid ester containing a hydroxyl group and an o-quinonediazide compound (Japanese Unexamined Patent Publication No.
No. 11546), a composition containing a polyamic acid ester and an o-quinonediazide compound (JP-A-2-18114).
No. 9) is known.

Meanwhile, the degree of integration of semiconductor elements has been improving year by year, and accordingly, improvement in fine processing technology has been desired. One of the technologies that enable microfabrication is to shorten the exposure wavelength in the lithography process, and the exposure light source for pattern formation using a positive photoresist is
The conventional g-line (436 nm) to i-line (365 nm) is becoming mainstream. For this reason, the photosensitive polyimide precursor is required to be able to form a pattern using the i-line as an exposure light source from the viewpoint of common use of an exposure apparatus. As the developer for the photosensitive polyimide precursor, as described above, an aqueous developer is desired in consideration of the environment. In particular, 2.38% by weight, which is generally used as a positive photoresist developer, is used.
When an aqueous solution of tetramethylammonium hydroxide can be used, in addition to the advantage that the load on the environment is small, there is an advantage that it is not necessary to change the development equipment. However,
When the above positive photosensitive polyimide precursor composition uses i-line as an exposure light source and uses a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developer, the thickness of the polyimide film after heat treatment is small. Even if a polyimide film having a large thickness is obtained, there is a problem that the exposure sensitivity for forming a pattern is low.

[0007]

The invention according to claims 1 to 3 has extremely high sensitivity to actinic rays such as i-rays,
An object of the present invention is to provide a positive photosensitive resin composition capable of forming a good pattern using an alkaline aqueous solution. According to a fourth aspect of the present invention, a 2.38% by weight aqueous solution of tetramethylammonium hydroxide, which is a general developer for a positive photoresist in a semiconductor device manufacturing process, has extremely high sensitivity to actinic rays such as i-rays. An object of the present invention is to provide a positive photosensitive resin composition which can be used to form a good pattern. The fifth aspect of the present invention provides a method for producing a relief pattern capable of forming a good relief pattern by exposing with an actinic ray such as i-ray and developing with an alkali developing solution.

[0008]

The present invention provides a positive photosensitive resin composition comprising (A) a polyimide precursor having a carboxyl group or a phenolic hydroxyl group and (B) a compound capable of generating an acid by light. A positive photosensitive resin composition in which the component (A) is a mixture of two kinds of polyimide precursors having a dissolution rate ratio to an aqueous alkali solution of 5 or more. In the present invention, the two kinds of polyimide precursors in the component (A) may each have the general formula (I)

Embedded image (Wherein R ¹ is a tetravalent organic group, R ² and R ³ are hydrocarbon groups, and R ⁴ is a divalent organic group having at least one phenolic hydroxyl group or carboxyl group) The present invention relates to the aforementioned positive photosensitive resin composition which is a polyamic acid ester.

Further, the present invention provides a compound of the formula (I) wherein R ¹ is an aromatic ring or two or three aromatic rings are a single bond, an ether bond, a 2,2-hexafluoropropylene bond, a sulfone bond, a methylene bond. And a tetravalent organic group having a chemical structure bonded via at least one bond selected from carbonyl bonds, wherein R ^{4 in the} general formula (I) is an aromatic ring or two to three aromatic rings. Single bond, ether bond, 2,2-
A divalent organic group having a chemical structure bonded via at least one bond selected from a hexafluoropropylene bond, a methylene bond and a sulfone bond, and having at least one phenolic hydroxyl group and / or carboxyl group; The present invention relates to the positive photosensitive resin composition. The present invention also relates to a positive photosensitive resin composition in which the alkaline aqueous solution is a 2.38% by weight aqueous solution of tetramethylammonium hydroxide. Furthermore, the present invention relates to a method for producing a relief pattern, which comprises applying the positive photosensitive resin composition on a substrate, drying, irradiating with an actinic ray, developing with an alkaline aqueous solution, and then heating. .

[0010]

DETAILED DESCRIPTION OF THE INVENTION (A) used in the present invention
The component is a polyimide precursor having a carboxyl group or a phenolic hydroxyl group, and is a mixture of two kinds of polyimide precursors having a dissolution rate ratio of 5 or more to an aqueous alkali solution, preferably an aqueous alkali solution used for development. As a polyimide precursor having a carboxyl group or a phenolic hydroxyl group, a polyamic acid ester having a carboxyl group or a phenolic hydroxyl group, a polyamic acid amide having a carboxyl group or a phenolic hydroxyl group, partially having a polyamic acid structure Examples thereof include polyamic acid esters or amides (that is, carboxyl groups remain). In the present invention, the two types of polyimide precursors include the polyamic acid ester having a repeating unit represented by the general formula (I). Is preferable because of having good developability.

In the general formula (I), the tetravalent organic group represented by R ¹ is a tetracarboxylic acid capable of reacting with a diamine to form a polyimide precursor, a dianhydride thereof, or a residue of a derivative thereof. It is preferably a group, specifically, a group containing an aromatic ring, and preferably 6 to 4 carbon atoms.
0 is more preferred. Examples of the group containing an aromatic ring include those containing one or more aromatic rings such as a benzene ring and a naphthalene ring. It is preferable that all of the four bonding sites in R ¹ are directly present on the aromatic ring. These binding sites are divided into two sets of two binding sites, and the two binding sites are preferably located at the ortho or peri position of the aromatic ring. The above two sets may be present on the same aromatic ring, or may be present on separate aromatic rings linked via various bonds. As the group containing an aromatic ring, the aromatic ring itself or two to three aromatic rings are a single bond, an ether bond, a methylene bond, an ethylene bond, a 2,2-propylene bond, a 2,2-hexafluoropropylene bond, a sulfone bond. And a tetravalent organic group having a chemical structure bonded through a sulfoxide bond, a thioether bond, a carbonyl bond, or the like.

In these, R ¹ is an aromatic ring or two or three aromatic rings selected from a single bond, an ether bond, a 2,2-hexafluoropropylene bond, a sulfone bond, a methylene bond and a carbonyl bond. Those obtained as the tetravalent organic group having a chemical structure bonded through at least one type of bond are preferable in terms of heat resistance and mechanical properties of the polyimide polymer after the heat treatment.

In the general formula (I), the divalent organic group having a carboxyl group or a phenolic hydroxyl group represented by R ⁴ is a carboxyl group or a divalent organic group which can react with a tetracarboxylic acid or a derivative thereof to form a polyimide precursor. It is preferably a residue of the diamine compound having a group or a phenolic hydroxyl group, excluding the amino group, preferably a group containing an aromatic ring, and having 6 to 6 carbon atoms excluding the carboxyl group.
40 are more preferred. As the group containing an aromatic ring,
Those containing one or more aromatic rings such as a benzene ring and a naphthalene ring are exemplified. Preferably, the two binding sites for R ⁴ are directly on the aromatic ring, in which case they may be on the same aromatic ring or on different aromatic rings. The carboxyl group or phenolic hydroxyl group is represented by R
It is preferable to have 1 to 8 in ² . As the group containing an aromatic ring, the aromatic ring itself or two to three aromatic rings are a single bond, an ether bond, a methylene bond, an ethylene bond, a 2,2-propylene bond, a 2,2-hexafluoropropylene bond,
Sulfone bond, sulfoxide bond, thioether bond,
Examples thereof include a divalent organic group having a chemical structure bonded via a carbonyl bond or the like and having at least one phenolic hydroxyl group and / or carboxyl group.

R ^{4 in the} general formula (I) is an aromatic ring or 2-3
Has a chemical structure in which the aromatic rings are bonded through at least one bond selected from a single bond, an ether bond, a 2,2-hexafluoropropylene bond, a methylene bond and a sulfone bond, and a phenolic hydroxyl group and A bivalent organic group having at least one carboxyl group is preferable from the viewpoint of heat resistance and mechanical properties of the polyimide polymer after the heat treatment. In the general formula (I),
The monovalent hydrocarbon group represented by R ² and R ³ is preferably a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl group, and more preferably an alkyl group having 1 to 8 carbon atoms.

The polyimide precursor having a repeating unit represented by the above general formula (I) further has a general formula (II)

Embedded image (Wherein R ¹ is a tetravalent organic group, R ² and R ³ are hydrocarbon groups, and R ⁵ is a divalent organic group having no phenolic hydroxyl group or carboxyl group). May be. In formula (II), 4-valent organic group represented by R ^1, hydrocarbon groups represented by R ² and R ³ are the same as the general formula (I).

The divalent organic group having no carboxyl group or phenolic hydroxyl group represented by R ⁵ is a carboxyl group or a phenolic hydroxyl group which can react with tetracarboxylic acid or a derivative thereof to form a polyimide precursor. The residue is preferably a residue obtained by removing an amino group of a diamine compound having no such group, preferably a group containing an aromatic ring, and more preferably a group having 6 to 40 carbon atoms. Examples of the group containing an aromatic ring include those containing one or more aromatic rings such as a benzene ring and a naphthalene ring. Two bonding sites of R ⁵ is preferably present directly on an aromatic ring, it may be present in this case on the same aromatic ring or different and be present on the aromatic ring. As the group containing an aromatic ring, the aromatic ring itself or two to three aromatic rings are a single bond, an ether bond, a methylene bond, an ethylene bond, a 2,2-propylene bond, a 2,2-
Examples include a divalent organic group having a chemical structure bonded through a hexafluoropropylene bond, a sulfone bond, a sulfoxide bond, a thioether bond, a carbonyl bond, or the like. R ^{5 in the} general formula (II) is at least one kind of an aromatic ring or two to three aromatic rings selected from a single bond, an ether bond, a 2,2-hexafluoropropylene bond, a methylene bond and a sulfone bond. Those which are divalent organic groups having a chemical structure bonded through a bond are preferable from the viewpoint of heat resistance and mechanical properties of the polyimide polymer after the heat treatment.

The component (A) may optionally have a repeating unit other than the repeating units represented by formulas (I) and (II). For example, in the general formula (I) or (II), a repeating unit in which a hydrogen atom is bonded instead of the monovalent hydrocarbon group represented by R ² or R ³ and the like can be mentioned.
In the component (A), the ratio of the repeating units of the general formulas (I) and (II) is m / (m + n), where m is the number of the former and n is the number of the latter. It is preferably 0.2, more preferably 1.0 to 0.4. When this value is less than 0.2, the solubility of the exposed portion of the film formed by coating and drying in an aqueous alkaline solution tends to be poor.

In the polyamic acid ester of the component (A), the total number of the repeating units of the general formulas (I) and (II) is 50% to 100% of the total number of the repeating units.
Is preferably 80% to 100%, more preferably 90% to 100%.
100% is particularly preferred. In addition, the repeating unit referred to here is one unit composed of one acid residue and one amine residue.

The molecular weight of each of the polyimide precursors of component (A) is 3,000 to 200,000 in terms of weight average molecular weight.
0 is preferable, and 5,000 to 100,000 is more preferable. The molecular weight can be measured by gel permeation chromatography and converted using a standard polystyrene calibration curve to obtain a value.

The component (A) of the present invention has the following general formula (II)
It can be obtained by reacting the tetracarboxylic diester dichloride represented by I) with a diamine compound represented by the following general formula (IV) and the following general formula (V).

Embedded image (Wherein R ¹ , R ² and R ³ in the formula are the same as in the general formula (I))

Embedded image (Wherein, R ⁴ in the formula is the same as general formula (I))

Embedded image (Wherein, R ⁵ in the formula is the same as general formula (II))

In this case, the reaction is carried out in the presence of a dehydrochlorination catalyst.
It is preferable to carry out in an organic solvent. The tetracarboxylic diester dichloride is represented by the following general formula (VIII) obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (VI) with an alcohol compound represented by the following general formula (VII). It can be obtained by reacting a tetracarboxylic diester with thionyl chloride.

[0022]

Embedded image (Where R ¹ in the formula is the same as in the general formula (I))

Embedded image (Where R ″ in the formula is a hydrocarbon group)

Embedded image (Wherein R ¹ , R ² and R ³ in the formula are the same as in the general formula (I))

The compound represented by the general formula (VI) is a tetracarboxylic dianhydride. However, from the viewpoint of heat resistance and mechanical properties of the polyimide polymer after the heat treatment, an aromatic group or a group of two or three Aromatic group is a single bond, ether bond, 2,2-
A carboxylic dianhydride having a chemical structure bonded via at least one bond selected from a hexafluoropropylene bond, a sulfone bond, a methylene bond and a carbonyl bond is preferable. Specific examples of these compounds include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-
Biphenyltetracarboxylic dianhydride, 2,2 ', 3
3'-biphenyltetracarboxylic dianhydride, 3,
3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic acid Dianhydride, 1,2,5,6-
Naphthalenetetracarboxylic dianhydride, 2,3,6,7
-Naphthalenetetracarboxylic dianhydride, 1,4,5
8-naphthalenetetracarboxylic dianhydride, 2,3
5,6-pyridinetetracarboxylic dianhydride, 3,4
9,10-perylenetetracarboxylic dianhydride, 2,2
Aromatic tetracarboxylic dianhydrides such as -bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride are preferred. These acid dianhydrides can be used alone or in combination of two or more.

Specific examples of the alcohol compound represented by the general formula (VII) include methanol, ethanol, n
-Propyl alcohol, isopropyl alcohol, n-
Butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, isoamyl alcohol, 1-hexanol, 2-hexanol,
Alkyl alcohols such as 3-hexanol can be mentioned as preferred, and they can be used alone or in combination of two or more.

The compound represented by the general formula (IV) is a diamine having at least one phenolic hydroxyl group and / or carboxyl group. However, from the viewpoint of heat resistance and mechanical properties of the polyimide polymer after heat treatment. An aromatic group or two or three aromatic groups having a single bond, an ether bond, 2,2-
Diamines having a chemical structure bonded via at least one bond selected from a hexafluoropropylene bond, a sulfone bond and a methylene bond are preferred. Specific examples of these compounds include 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,5-diaminoterephthalic acid, and bis (4-amino-3-carboxy) Phenyl) methylene, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4 '
-Diamino-5,5'-dicarboxy-2,2'-dimethylbiphenyl, 1,3-diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene,
3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl)
Sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4-amino-3
-Hydroxyphenyl) hexafluoropropane, bis (4-amino-3-carboxyphenyl) methane and the like. These diamine compounds having at least one phenolic hydroxyl group and / or carboxyl group can be used alone or in combination of two or more.

The compound represented by the above general formula (V) is a diamine, but from the viewpoint of heat resistance and mechanical properties of the polyimide-based polymer after the heat treatment, an aromatic group or a few aromatic groups are simply formed. Diamines having a chemical structure bonded via at least one bond selected from a bond, an ether bond, a 2,2-hexafluoropropylene bond, a sulfone bond and a methylene bond are preferred. Specific examples of these compounds include 4,4'-diaminodiphenyl ether,
4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (3-
Aminophenoxyphenyl) sulfone, 1,4-bis (4-aminophenoxy) benzene, 4,4'-diamino-2,2'-dimethylbiphenyl, and the like. These diamine compounds can be used alone or in combination of two or more.

A method for synthesizing the tetracarboxylic acid diester compound represented by the general formula (VIII) is known. For example, tetracarboxylic dianhydride and an excess of the alcohol compound represented by the general formula (VII) are used. Are mixed, heated and reacted, and then the excess alcohol compound is removed. The preferred ratio (molar ratio, former / latter) of carboxylic dianhydride to alcohol compound is 1
/ 2 to 1/20, more preferably 1/20.
The range is 2.5 to 1/10. The preferred reaction temperature is 30 to 130 ° C, and the preferred reaction time is 3 to 24 hours. A method for synthesizing tetracarboxylic diester dichloride is known. For example, it is obtained by reacting tetracarboxylic diester with excess thionyl chloride by heating and then removing excess thionyl chloride. The preferred ratio (molar ratio) of the tetracarboxylic diester to excess thionyl chloride is in the range of 1/2 to 1/10, and the more preferred ratio is in the range of 1 / 2.2 to 1/5. The preferred reaction temperature is 0 to 100 ° C, and the preferred reaction time is 1
-10 hours.

The polymer as the component (A) is prepared by dissolving a diamine compound represented by the general formulas (IV) and (V) and a dehydrochlorination catalyst such as pyridine in an organic solvent.
It is obtained by dropping and reacting tetracarboxylic diester dichloride dissolved in an organic solvent, then pouring the mixture into a poor solvent such as water, and filtering and drying the precipitate. As the organic solvent used for the reaction, for example, N-methyl-2
-Pyrrolidone, N, N-dimethylformamide, N, N
-Dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, tetramethylenesulfone, γ
-Aprotic polar solvents such as butyrolactone are used alone or in combination of two or more.

The preferable ratio (molar ratio) of the total amount of the diamine compounds represented by the above general formulas (IV) and (V) to the tetracarboxylic diester dichloride is 0.95 / 1 to 1 / l in the former / latter. The range is 0.95. The preferred reaction temperature is -30 to 40 ° C, and the preferred reaction time is 5 minutes to 10 hours. The preferable ratio of the dehydrochlorination catalyst to the tetracarboxylic diester dichloride is such that the former / the latter (molar ratio) is in the range of 0.95 / 1 to 1 / 0.95.

The two kinds of polyimide precursors used in the present invention have a dissolution rate ratio of 5 or more to an aqueous alkali solution, preferably an aqueous alkali solution actually used for development. When the dissolution rate ratio is less than 5, there is a disadvantage that the film thickness of the polyimide film after the heat treatment becomes small, or the exposure sensitivity for pattern formation becomes low even if a polyimide film having a large film thickness is obtained. In the same point, the dissolution rate ratio is preferably 7 or more, and more preferably 7 to 100. The dissolution rate is determined by dissolving the polyimide precursor in a solvent (e.g., the solvent (C) described below), applying the solution to the substrate, drying the applied solution, and then spraying an aqueous alkali solution to dissolve the polyimide precursor film. The required time (seconds) is obtained by dividing the thickness of the polyimide precursor after coating and drying.

As for the dissolution rate, one of the dissolution rates is 0.1 to 10 nm in terms of exposure sensitivity and film thickness after development.
/ Sec, and the other is preferably 10-100
It is preferably 0 nm / sec. Here, the dissolution rate can be measured, for example, as follows. First, a positive photosensitive resin composition is applied to a silicon substrate by spin coating, and dried on a hot plate to form a film of 5 to 7 μm. Next, the alkaline aqueous solution is bathed on the film of the positive photosensitive resin composition in a shower form, and is left for an appropriate standing time, for example, 2.38.
In the case of using an aqueous solution of tetramethylammonium hydroxide by weight, the substrate was left for 50 seconds, immersed in pure water to remove the alkaline aqueous solution from the film, and then rotated at 3,000 rpm for 30 minutes.
Rotate for 2 seconds to shake off pure water. When the film is completely dissolved within the leaving time after being immersed in the alkali aqueous solution, the film thickness after drying is divided by the time required for dissolution to obtain the dissolution rate. When the film is not completely dissolved even after the elapse of the standing time, the thickness reduced by the dissolution is divided by the standing time to obtain the dissolution rate.

The alkaline aqueous solution in the present invention is, for example, an aqueous solution of 5% by weight or less of sodium hydroxide, potassium hydroxide, sodium silicate, tetramethylammonium hydroxide or the like, preferably 1.5 to 3.
An aqueous solution of 0% by weight or the like can be mentioned, but it is preferably an aqueous solution of 1.5 to 3.0% by weight of tetramethylammonium hydroxide, which is frequently used in a positive resist.
Most preferably, it is a 2.38% by weight aqueous solution of tetramethylammonium hydroxide.

There are no particular restrictions on the method for producing these two kinds of polyimide precursors. For example, among the above-mentioned preferred tetracarboxylic dianhydrides, diamines and the like, different ones may be used for the respective raw materials, It can be adjusted by changing the ratio of each of the repeating units represented by the general formula (I), changing the molecular weight, and the like. 2
The mixing ratio of the kind of polyimide precursor is appropriately determined according to the kind of the compound which generates an acid by light as the component (B), its amount, and the like. 9
7 to 97/3, preferably 5/95 to 95 /
More preferably, it is 5. In the present invention,
The component (A) may further contain components other than the above two types, but the amount is preferably 20% by weight or less based on the total amount of the component (A).

The compound which generates an acid by light, which is the component (B) used in the present invention, is a photosensitizer, and is preferably a compound which generates a carboxylic acid by light, and an o-quinonediazide compound is excellent in its effect. preferable. The o-quinonediazide compound can be obtained, for example, by subjecting o-quinonediazidosulfonyl chlorides to a condensation reaction with a hydroxy compound, an amino compound and the like in the presence of a dehydrochlorinating catalyst. Examples of o-quinonediazidosulfonyl chlorides include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, naphthoquinone-1,
2-diazide-4-sulfonyl chloride and the like can be used.

Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2
2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone,
2,3,4,4'-tetrahydroxybenzophenone,
2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,2', 3'-pentahydroxybenzophenone, 2,3,4,3 ', 4', 5'-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro-1,3,6,8-tetrahydroxy-5 1
Examples include 0-dimethylindeno [2,1-a] indene, tris (4-hydroxyphenyl) methane, and tris (4-hydroxyphenyl) ethane.

As the amino compound, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-
Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, o-aminophenol, m-aminophenol, p-aminophenol, 3,3'-diamino -4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, Bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4
-Amino-3-hydroxyphenyl) hexafluoropropane and the like.

The o-quinonediazidosulfonyl chloride and the hydroxy compound or the amino compound may be blended so that the total of the hydroxy group and the amino group is 0.5 to 1 equivalent per 1 mol of the o-quinonediazidosulfonyl chloride. preferable. The preferred ratio of the dehydrochlorination catalyst to o-quinonediazide sulfonyl chloride is 0.95 / 1 to 0.95 / 1.
The range is 1 / 0.95. The preferred reaction temperature is 0 to
At 40 ° C., the preferred reaction time is 1 to 10 hours.

As the reaction solvent, for example, solvents such as dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone and the like are used. Examples of the catalyst for dehydrochlorination include sodium carbonate, sodium hydroxide, sodium hydrogencarbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like. In the present invention, the ratio of the component (B) to the component (A) is appropriately determined, but from the viewpoint of the difference in solubility between the exposed and unexposed portions and the allowable width of the sensitivity, the component (A) 1
Component (B) is preferably 5 to 100 parts by weight, more preferably 10 to 40 parts by weight, based on 00 parts by weight.

The photosensitive resin composition of the present invention is usually obtained by dissolving the components (A) and (B) in a solvent (C) and can be obtained in a solution state. Examples of the solvent include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone, γ-butyrolactone, cyclohexanone, and cyclopentanone Aprotic polar solvents are used alone or in combination of two or more. Although the amount of the solvent (C) is not particularly limited, it is usually used in an amount of 40 to 400 parts by weight based on the total of the components (A) and (B).

The positive photosensitive resin composition of the present invention preferably further contains an organic silane compound, an aluminum chelate compound, a silicon-containing polyamic acid and the like as an adhesion assistant. Examples of the organic silane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and the like. Can be

As the aluminum chelate compound, for example,
Tris (acetylacetonate) aluminum, acetyl acetate aluminum diisopropylate and the like can be mentioned.

Examples of the silicon-containing polyamic acid include a polymer obtained by reacting a tetracarboxylic dianhydride represented by the general formula (VI) with a diamine compound represented by the following formula in a solution.

[0043]

Embedded image

When these are used, the amount varies depending on the type, but from the viewpoint of the adhesion between the formed film and the substrate and the allowable width of the remaining film ratio, 100 parts by weight of the component (A) is used.
The amount is preferably 1 to 50 parts by weight, more preferably 2 to 20 parts by weight.

The positive photosensitive resin composition of the present invention can be used for a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ ,
SiO ₂ etc.), applied on a supporting substrate such as silicon nitride,
By drying, a film of the positive photosensitive resin composition can be obtained. After that, irradiation with actinic rays such as ultraviolet rays, visible rays, and radiations is performed through a mask, and then the exposed portions are removed with a developer to obtain a positive relief pattern. Since the positive photosensitive composition of the present invention exhibits excellent characteristics particularly for i-line exposure, it is preferable to perform exposure with i-line.

Drying is usually performed using an oven or a hot plate. Drying conditions are appropriately determined according to the components of the positive photosensitive resin composition. When a hot plate is used, drying is preferably performed at 60 to 140 ° C. for 30 seconds to 10 minutes. If the drying temperature is low, the solvent will not evaporate sufficiently,
It tends to contaminate the exposure apparatus and the like. When the drying temperature is high, the post-o-quinonediazide compound in the film of the positive photosensitive resin composition tends to decompose during drying.

As the developing solution, it is preferable to use an alkali developing solution. For example, an aqueous solution of 5% by weight or less such as sodium hydroxide, potassium hydroxide, sodium silicate and tetramethylammonium hydroxide, preferably 1.5% by weight. ~
A 3.0% by weight aqueous solution or the like is used, and a more preferred developer is 1.5 to 1.5% by weight of tetramethylammonium hydroxide.
It is a 3.0% by weight aqueous solution. Further, an alcohol or a surfactant may be added to the above-mentioned developer for use. These are each based on 100 parts by weight of the developing solution.
Preferably 0.01 to 10 parts by weight, more preferably 0.1 to 10 parts by weight.
It is blended in the range of 1 to 5 parts by weight. Next, the resulting relief pattern is subjected to a heat treatment at 150 to 450 ° C. to form a relief pattern of a heat-resistant polymer having a cyclic group such as an imide ring or an isoindoloquinazoline ring.

[0048]

The present invention will be described below in more detail with reference to examples. Example 1 In a 0.5 liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, 24.82 g of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, n-
59.30 g of butyl alcohol was charged and reacted at 95 ° C. with stirring for 5 hours. Excess n-butyl alcohol was distilled off under reduced pressure to obtain 3,3 ', 4,4'-diphenylethertetracarboxylic acid di-n-butyl ester. Next, 95.17 g of thionyl chloride and 70.00 g of toluene were charged into the flask and reacted at 40 ° C. for 3 hours. Excessive thionyl chloride is azeotroped with toluene under reduced pressure,
Removed. 186 g of N-methylpyrrolidone are added,
A solution (α) of 3,3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-butyl ester dichloride was obtained.

Next, 95 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, and 7.91 g of 3,5-diaminobenzoic acid and 4,4'- After adding 5.61 g of diaminodiphenyl ether, stirring and dissolving, pyridine 12.
66 g was added, and while maintaining the temperature at 0 to 5 ° C, 3,
A solution (α) of 3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-butyl ester dichloride was added dropwise over 1 hour, and stirring was continued for 1 hour. The solution was poured into 4 liters of water, the precipitate was collected, washed, and dried under reduced pressure to obtain a polyamic acid n-butyl ester (hereinafter, referred to as polymer I). This polymer was dissolved in N-methylpyrrolidone, applied by a spin coating method, dried, and sprayed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide to measure the dissolution rate in the aqueous solution.
2.6 nm / sec. The weight-average molecular weight measured by gel permeation chromatography was 23,000.

On the other hand, 95 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, and 3,5-diaminobenzoic acid was added.
13 g, 4,4'-diaminodiphenyl ether 4.0
After adding and dissolving with stirring, 12.66 g of pyridine was added.
And keeping the temperature at 0 to 5 ° C,
4,4'-diphenylethertetracarboxylic acid di-n-
After the solution (α) of butyl ester dichloride was added dropwise for 1 hour, stirring was continued for 1 hour. The solution was poured into 4 liters of water, and the precipitate was collected, washed, and dried under reduced pressure to obtain a polyamic acid n-butyl ester (hereinafter, polymer II).
And). This polymer was dissolved in N-methylpyrrolidone, applied by a spin coating method, dried and sprayed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide to measure the dissolution rate in the aqueous solution.
nm / sec. When the weight average molecular weight was measured by gel permeation chromatography,
4,200.

15.00 g of polymer I, polymer II
15.00 g, 2,3,4,4'-tetrahydroxybenzophenone and naphthoquinone-1,2-diazide-5
7.50 g of a compound obtained by reacting sulfonyl chloride at a molar ratio of 1/3 was dissolved under stirring in 54.00 g of NMP.
This solution was filtered under pressure using a Teflon filter having a pore size of 3 μm to obtain a positive photosensitive composition. The obtained positive photosensitive composition is spin-coated on a silicon wafer using a spinner, and dried by heating on a hot plate at 125 ° C. for 3 minutes to form a 6.8 μm film of the positive photosensitive resin composition. Obtained. An i-line reduction projection exposure apparatus (LD-5010i, manufactured by Hitachi, Ltd.) was applied to this coating film to form a coating film 600 through a mask.
Exposure was performed at mJ / cm ² . Subsequently, paddle development was performed for 70 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution, followed by washing with pure water to obtain a relief pattern. The film thickness after development was 5.5 μm. Next, the pattern is heated at 350 ° C. for 1 hour in a nitrogen atmosphere,
A 3.6 μm thick polyimide film pattern was obtained.

Example 2 28.66 g of 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride was placed in a 0.5-liter flask equipped with a stirrer, thermometer and Dimroth condenser, and n −
59.30 g of butyl alcohol was charged and reacted at 95 ° C. with stirring for 5 hours. Excess n-butyl alcohol was distilled off under reduced pressure to obtain 3,3 ', 4,4'-diphenylsulfonetetracarboxylic acid di-n-butyl ester. Next, 95.17 g of thionyl chloride and 70.00 g of toluene were charged into the flask and reacted at 40 ° C. for 3 hours. Excessive thionyl chloride is azeotroped with toluene under reduced pressure,
Removed. 186 g of N-methylpyrrolidone are added,
A solution (β) of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid di-n-butyl dichloride was obtained.

Next, 95 g of N-methylpyrrolidone was charged into a 0.5-liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, and 8.28 g of 3,5-diaminobenzoic acid and 4,4'- 5.13 g of diaminodiphenyl ether was added and dissolved by stirring.
66 g was added, and while maintaining the temperature at 0 to 5 ° C, 3,
A solution (β) of 3 ′, 4,4′-diphenylsulfonetetracarboxylic acid di-n-butyl ester dichloride was added dropwise over 1 hour, and then stirring was continued for 1 hour. The solution was poured into 4 liters of water, the precipitate was collected, washed, and dried under reduced pressure to obtain a polyamic acid n-butyl ester (Polymer II)
I). The polymer was dissolved in N-methylpyrrolidone, applied by a spin coating method, dried, and sprayed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide to measure the dissolution rate in the aqueous solution.
It was 0 nm / sec. Also, when the weight average molecular weight was measured by gel permeation chromatography,
19,700.

On the other hand, 95 g of N-methylpyrrolidone was charged into a 0.5-liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, and 3,5-diaminobenzoic acid was added.
25 g, 4,4'-diaminodiphenyl ether 3.8
After adding 5 g and dissolving with stirring, 12.66 g of pyridine was added.
And keeping the temperature at 0 to 5 ° C,
4,4'-diphenylsulfonetetracarboxylic acid di-n-
After the butyl ester dichloride solution (β) was added dropwise over 1 hour, stirring was continued for 1 hour. The solution was poured into 4 liters of water, and the precipitate was collected, washed, and dried under reduced pressure to obtain a polyamic acid n-butyl ester (referred to as polymer IV). This polymer is dissolved in N-methylpyrrolidone,
The solution was applied by a spin coating method, dried, and sprayed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide to measure the dissolution rate in the aqueous solution.
/ Sec. When the weight-average molecular weight was measured by gel permeation chromatography,
7,600.

24.0 g of polymer III, polymer IV
6.0 g, 9.00 g of a compound obtained by reacting 4,4′-diaminodiphenyl sulfone with naphthoquinone-1,2-diazido-5-sulfonyl chloride in a molar ratio of 1/2,
It was dissolved by stirring in 54.00 g of NMP. 3 μm of this solution
The mixture was filtered under pressure using a Teflon filter having pores to obtain a positive photosensitive composition. The obtained positive photosensitive composition is spin-coated on a silicon wafer using a spinner, and dried by heating at 100 ° C. for 3 minutes on a hot plate to obtain 6.4 μm.
m was obtained as a positive photosensitive resin composition film. This coating has i
Line reduction projection exposure system (LD-501 manufactured by Hitachi, Ltd.)
Using 0i), exposure was performed at 500 mJ / cm ² through a mask. Next, paddle development was performed for 90 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution.
After washing with pure water, a relief pattern was obtained. The film thickness after development was 5.2 μm. Next, this pattern was subjected to a heat treatment at 350 ° C. for 1 hour in a nitrogen atmosphere to obtain a 3.3 μm-thick polyimide film pattern.

Example 3 In a 0.5 liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, 17.4 pyromellitic dianhydride was placed.
5 g and n-butyl alcohol 59.30 g were charged, and 95
The mixture was stirred and reacted at 5 ° C. for 5 hours. Excess n-butyl alcohol was distilled off under reduced pressure to obtain pyronellitic acid di-n-butyl ester. Next, 95.17 g of thionyl chloride and 70.00 g of toluene were charged into the flask and reacted at 40 ° C. for 3 hours. Excess thionyl chloride was azeotroped with toluene under reduced pressure and removed. 186 g of N-methylpyrrolidone was added to obtain a solution (γ) of di-n-butyl pyromellitic acid dichloride.

Next, 95 g of N-methylpyrrolidone was charged into a 0.5-liter flask equipped with a stirrer, thermometer, and Dimroth condenser, and bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added. 75
g, 4,4'-diaminodiphenyl sulfone 7.15 g
Was added thereto, and the mixture was stirred and dissolved. Then, 12.66 g of pyridine was added, and while maintaining the temperature at 0 to 5 ° C, a solution (γ) of di-n-butyl pyromellitic acid dichloride was added dropwise over 1 hour. Stirring was continued for hours. The solution was poured into 4 liters of water, and the precipitate was collected, washed, and dried under reduced pressure to obtain a polyamic acid n-butyl ester (hereinafter, referred to as polymer V). This polymer was dissolved in N-methylpyrrolodone, applied by a spin coating method, dried, and sprayed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide to measure the dissolution rate in the aqueous solution.
2.1 nm / sec. The weight-average molecular weight measured by gel permeation chromatography was 31,600.

On the other hand, 95 g of N-methylpyrrolidone was charged into a 0.5-liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, and bis (3-amino-4-hydroxyphenyl) hexafluoropropane. 80g,
After adding 5.76 g of 4,4'-diaminodiphenylsulfone and dissolving with stirring, 12.66 g of pyridine is added, and while maintaining the temperature at 0 to 5 ° C., dimerro pyromellitic acid is added.
After the solution (γ) of -butyl ester dichloride was added dropwise for 1 hour, stirring was continued for 1 hour. The solution was poured into 4 liters of water, and the precipitate was collected, washed, and dried under reduced pressure to obtain a polyamic acid n-butyl ester (hereinafter referred to as polymer).
VI). This polymer was dissolved in N-methylpyrrolidone, applied by a spin coating method, dried, and sprayed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide to measure the dissolution rate in the aqueous solution.
It was 5.5 nm / sec. The weight-average molecular weight measured by gel permeation chromatography was 33,500.

9.00 g of polymer V, polymer VI 2
1.00 g of compound 6.0 obtained by reacting tris (4-hydroxyphenyl) methane with naphthoquinone-1,2-diazide-5-sulfonyl chloride in a molar ratio of 1 / 2.5.
0 g was dissolved under stirring in 54.00 g of NMP. This solution was filtered under pressure using a Teflon filter having a pore size of 3 μm to obtain a positive photosensitive composition. The obtained positive photosensitive composition is spin-coated on a silicon wafer using a spinner, and dried by heating at 90 ° C. for 3 minutes on a hot plate.
A 6.4 μm film of the positive photosensitive resin composition was obtained. An i-line reduction projection exposure apparatus (LD manufactured by Hitachi, Ltd.)
Using -5010i), exposure was performed at 400 mJ / cm ² through a mask. Subsequently, paddle development was performed for 70 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution, followed by washing with pure water to obtain a relief pattern. The film thickness after development was 5.6 μm. Next, this pattern was subjected to a heat treatment at 350 ° C. for 1 hour in a nitrogen atmosphere.
A polyimide film pattern of 5 μm was obtained.

Comparative Example 1 In a 0.5 liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, 24.82 g of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, n-
59.30 g of butyl alcohol was charged and reacted at 95 ° C. with stirring for 5 hours. Excess n-butyl alcohol was distilled off under reduced pressure to obtain 3,3 ', 4,4'-diphenylethertetracarboxylic acid di-n-butyl ester. Next, 95.17 g of thionyl chloride and 70.00 g of toluene were charged into the flask and reacted at 40 ° C. for 3 hours. Excessive thionyl chloride is azeotroped with toluene under reduced pressure,
Removed. 186 g of N-methylpyrrolidone are added,
A solution (δ) of 3,3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-butyl ester dichloride was obtained.

Next, 95 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, and 7.30 g of 3,5-diaminobenzoic acid, 4,4'- 6.41 g of diaminodiphenyl ether was added, and the mixture was stirred and dissolved.
66 g was added, and while maintaining the temperature at 0 to 5 ° C, 3,
A solution (δ) of 3 ′, 4,4′-diphenylethertetracarboxylic acid di-n-butyl ester dichloride was added dropwise over 1 hour, and stirring was continued for 1 hour. The solution was poured into 4 liters of water, the precipitate was collected, washed, and dried under reduced pressure to obtain a polyamic acid n-butyl ester (hereinafter, referred to as polymer VII). This polymer was dissolved in N-methylpyrrolidone, applied by a spin coating method, dried and sprayed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide to measure the dissolution rate in the aqueous solution. there were. The weight-average molecular weight measured by gel permeation chromatography was 22,900.

30.00 g of polymer VII, 2,3
4,4'-tetrahydroxybenzophenone and naphthoquinone-1,2-diazido-5-sulfonyl chloride
7.50 g of the compound reacted at a molar ratio of
The mixture was dissolved in 54.00 g with stirring. This solution was filtered under pressure using a Teflon filter having a pore size of 3 μm to obtain a positive photosensitive composition. The obtained positive photosensitive composition is spin-coated on a silicon wafer using a spinner, and dried by heating on a hot plate at 125 ° C. for 3 minutes to form a 6.8 μm film of the positive photosensitive resin composition. Obtained. An i-line reduction projection exposure apparatus (LD-5010i manufactured by Hitachi, Ltd.) is applied to this coating film.
Was exposed through a mask at 1000 mJ / cm ² .
Subsequently, paddle development was performed for 70 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution, followed by washing with pure water to obtain a relief pattern. The film thickness after development was 5.0 μm. Next, this pattern was subjected to a heat treatment at 350 ° C. for 1 hour in a nitrogen atmosphere to obtain a 3.2 μm-thick polyimide film pattern. As can be seen from the above Examples and Comparative Examples, in Examples of the present invention, the sensitivity to i-ray was excellent, and development was possible with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide. The sensitivity was poor, and development was not possible without increasing the exposure.

Comparative Example 2 Pyromellitic dianhydride 17.4 was placed in a 0.5-liter flask equipped with a stirrer, thermometer, and Dimroth condenser.
5 g, n-butyl alcohol 59.30 g, 95
The mixture was stirred and reacted at 5 ° C. for 5 hours. Excess n-butyl alcohol was distilled off under reduced pressure to obtain pyronellitic acid di-n-butyl ester. Next, 95.17 g of thionyl chloride and 70.00 g of toluene were charged into the flask and reacted at 40 ° C. for 3 hours. Excess thionyl chloride was azeotroped with toluene under reduced pressure and removed. 186 g of N-methylpyrrolidone was added to obtain a solution (ε) of pyromellitic acid di-n-butyl ester dichloride.

Next, 95 g of N-methylpyrrolidone was charged into a 0.5-liter flask equipped with a stirrer, thermometer, and Dimroth condenser, and bis (3-amino-4-hydroxyphenyl) hexafluoropropane was 19.63.
g, 4,4'-diaminodiphenyl sulfone 6.55 g
Was added and stirred and dissolved. Then, 12.66 g of pyridine was added, and while maintaining the temperature at 0 to 5 ° C, a solution (ε) of di-n-butyl pyromellitic acid dichloride was added dropwise over 1 hour. Stirring was continued for hours. The solution was poured into 4 liters of water, the precipitate was collected, washed, and dried under reduced pressure to obtain a polyamic acid n-butyl ester (hereinafter referred to as polymer).
VIII). This polymer was dissolved in N-methylpyrrolidone, applied by a spin coating method, dried and sprayed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide to measure the dissolution rate in the aqueous solution.
It was 2 nm / sec. The weight average molecular weight was measured by gel permeation chromatography.
It was 0,800.

On the other hand, 95 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, and 20.51 g of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was charged. ,
After adding 4.96 g of 4,4'-diaminodiphenyl sulfone and stirring and dissolving, 12.66 g of pyridine is added.
A solution (ε) of -butyl ester dichloride was added dropwise over 1 hour, and then stirring was continued for 1 hour. The solution was poured into 4 liters of water, and the precipitate was collected, washed, and dried under reduced pressure to obtain a polyamic acid n-butyl ester (hereinafter referred to as polymer).
IX). This polymer was dissolved in N-methylpyrrolidone, applied by a spin coating method, dried and sprayed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide, and the dissolution rate in the aqueous solution was measured.
0.3 nm / sec. The weight-average molecular weight measured by gel permeation chromatography was 32,100.

12.00 g of polymer VIII, polymer IX
18.00 g, compound 4.5 obtained by reacting tris (4-hydroxyphenyl) methane with naphthoquinone-1,2-diazido-5-sulfonyl chloride in a molar ratio of 1/3.
0 g was dissolved in 54.00 g of NMP with stirring. This solution was filtered under pressure using a Teflon filter having a pore size of 3 μm to obtain a positive photosensitive composition. The obtained positive photosensitive composition is spin-coated on a silicon wafer using a spinner, and dried by heating at 100 ° C. for 3 minutes on a hot plate to form a 6.4 μm film of the positive photosensitive resin composition. Obtained.
An i-line reduction projection exposure system (L, manufactured by Hitachi, Ltd.)
1-50 mJ / cm ² through a mask using D-5010i)
Was exposed. Subsequently, paddle development was performed for 100 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution, followed by washing with pure water to obtain a relief pattern.
The film thickness after development was 5.4 μm. Next, this pattern was subjected to a heat treatment at 350 ° C. for 1 hour in a nitrogen atmosphere to obtain a 3.3 μm-thick polyimide film pattern.

[0067]

The positive photosensitive resin compositions according to claims 1, 2 and 3 have a very high sensitivity to actinic rays such as i-rays and can form a good pattern using an alkaline aqueous solution. It is. Therefore, it is most suitable for a positive photosensitive resin composition for forming a surface protective film, an interlayer insulating film and the like of a semiconductor element and the like. The positive photosensitive resin composition according to claim 4 has extremely high sensitivity to actinic rays such as i-rays,
A good pattern can be formed using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide, which is a general developing solution of a positive photoresist in a semiconductor device manufacturing process. Therefore, it is most suitable for a positive photosensitive resin composition for forming a surface protective film, an interlayer insulating film and the like of a semiconductor element and the like. According to the method for producing a relief pattern according to the fifth aspect, it is possible to form a good relief pattern by exposing with an actinic ray such as i-ray and developing with an alkali developer. Therefore, surface protection films for semiconductor devices and the like can be easily formed.
An interlayer insulating film or the like can be formed.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takanori Ansai 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside the Yamazaki Plant of Hitachi Chemical Co., Ltd. No. 1 Hitachi Chemical Co., Ltd. Yamazaki Plant

Claims (5)

[Claims] 1. A positive photosensitive resin composition comprising (A) a polyimide precursor having a carboxyl group or a phenolic hydroxyl group and (B) a compound capable of generating an acid by light, wherein the component (A) comprises: A positive photosensitive resin composition which is a mixture of two kinds of polyimide precursors having a dissolution rate ratio to an alkaline aqueous solution of 5 or more. 2. The two kinds of polyimide precursors in the component (A) are each represented by the general formula (I): (Wherein R ¹ is a tetravalent organic group, R ² and R ³ are hydrocarbon groups, and R ⁴ is a divalent organic group having at least one phenolic hydroxyl group or carboxyl group) The positive photosensitive resin composition according to claim 1, which is a polyamic acid ester. 3. The method according to claim 1, wherein R ^{1 in the} formula (I) is an aromatic ring or 2-3.
Having a chemical structure in which two aromatic rings are bonded via at least one bond selected from a single bond, an ether bond, a 2,2-hexafluoropropylene bond, a sulfone bond, a methylene bond, and a carbonyl bond. Wherein R ^{4 in} formula (I) is an aromatic ring or two or three aromatic rings selected from a single bond, an ether bond, a 2,2-hexafluoropropylene bond, a methylene bond and a sulfone bond. The positive photosensitive resin composition according to claim 2, which is a divalent organic group having a chemical structure bonded through at least one type of bond and having at least one phenolic hydroxyl group and / or carboxyl group. 4. The aqueous alkaline solution is a 2.38% by weight aqueous solution of tetramethylammonium hydroxide.
Or a positive photosensitive resin composition according to item 3. 5. The positive photosensitive resin composition according to claim 1, 2, 3 or 4, coated on a substrate, dried, irradiated with actinic rays, developed with an aqueous alkali solution, and then heat-treated. A method for producing a relief pattern, characterized in that: