JPH10239844A - Heat-resistant photosensitive polymer composition and manufacture of relief pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the heat-resistant positive photosensitive polymer composition high in sensitivity and the film endurance of a nonexposed part by incorporating a specified polyamido acid ester and the like. SOLUTION: This heat-resistant photosensitive polymer composition contains the polyamido acid ester having repeating units each represented by formula I and an o-quinonediazido compound and a compound represented by formula II, and in formulae I and II, R<1> is a tetravalent organic group; R<2> is a divalent organic group having a carboxylic group or a phenolic hydroxyl group; R<3> is a univalent organic group; and each of R<4> and R<5> is an alkyl group. The tetravalent organic group is a residue of a tetracarboxylic acid or its dianhydride or its derivative for producing a polyimide or polyimidoisoindoloquinazolindione. The divalent organic group having a carboxylic acid or a phenolic hydroxyl group is a residue obtained by removing the amino group of the diamine compound having a carboxylic acid or a phenolic hydroxyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant photosensitive polymer composition and a method for producing a relief pattern. The present invention relates to a positive heat-resistant photosensitive polymer composition which can be used as 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. There is known a composition to which a compound containing a double bond and an amino group and an aromatic bis azide is added (Japanese Patent Publication No. 3-36861).

In using the photosensitive polyimide composition, usually, it is applied on a substrate in a solution state, dried, irradiated with an actinic ray through a mask, and the exposed portion is removed with a developing solution to form a pattern. However, the composition is negative-working and uses an organic solvent for development. Therefore, in order to switch from an etching process using a positive photoresist to a negative photosensitive polyimide, there is a problem that a mask of an exposure apparatus and development equipment need to be changed.

On the other hand, as for the positive photosensitive polyimide, a polyimide precursor having an o-nitrobenzyl group introduced through an ester bond (Japanese Patent Application Laid-Open No. 60-37550), a polyamide acid ester containing a carboxyl group and o-
-A composition containing a quinonediazide compound (JP-A-4-16
No. 8411) and a composition containing a polyamic acid and a nifedipine compound (JP-A-5-5995). However, the former has a problem that the sensitivity is low because the wavelength to be exposed is mainly 300 nm or less, and the middle has a problem that adhesion between the formed film and the substrate is poor,
The latter has a small dissolution rate difference between the exposed part and the unexposed part,
There is a problem that the unexposed portion residual film ratio after development is poor. As described above, at present, a positive photosensitive polyimide having sufficient characteristics has not been obtained.

[0006]

SUMMARY OF THE INVENTION The present invention overcomes the above-mentioned problems of the prior art. That is, the first aspect of the present invention provides a positive heat-resistant photosensitive polymer composition having high sensitivity and a high unexposed portion residual film ratio. The second aspect of the present invention provides a method for producing a relief pattern having a high sensitivity and a high unexposed portion residual film ratio.

[0007]

According to the present invention, there is provided a compound represented by the following general formula (I):

Embedded image (Wherein, R ¹ represents a tetravalent organic group, R ² represents a divalent organic group having a carboxyl group or a phenolic hydroxyl group, and R ³ represents a monovalent organic group). Polyamic acid ester having units, (b) o-quinonediazide compound and (c) general formula (II)

Embedded image (Wherein, R ⁴ and R ⁵ each represent an alkyl group).

The present invention also relates to a method for producing a relief pattern including a step of applying and drying the heat-resistant photosensitive polymer composition on a support substrate, a step of exposing, a step of developing, and a step of heating.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The component (a) in the present invention is a polyamic acid ester having a repeating unit represented by the aforementioned general formula (I). In the general formula (I), R ¹
The tetravalent organic group represented by is a residue of tetracarboxylic acid, a dianhydride or a derivative thereof, which is a raw material of polyimide or polyimide isoindoloquinazolinedione, and is a tetravalent aromatic group or an aliphatic group. Is preferable, and those having 4 to 40 carbon atoms are more preferable, and those having 4 to 40 carbon atoms are preferable.
40 tetravalent aromatic groups are more preferred. The tetravalent aromatic group preferably includes an aromatic ring (a benzene ring, a naphthalene ring, etc.), and all four binding sites are formed from an aromatic ring. Preferably, these binding sites are divided into two sets of two binding sites, and the two binding sites are located on adjacent carbons of the aromatic ring (ie, those located at the ortho position). The two sets may be from the same aromatic ring, or may be from separate aromatic rings linked through various bonds.

In the general formula (I), the divalent organic group having a carboxyl group or a phenolic hydroxyl group represented by R ² is a residue excluding the amino group of a diamine compound having a carboxyl group or a phenolic hydroxyl group. Yes, an aromatic group or an aliphatic group is preferable, one having 2 to 40 carbon atoms excluding a carboxyl group is more preferable, and an aromatic group is further preferable. Here, the aromatic group includes an aromatic ring (benzene ring, naphthalene ring, etc.), and it is preferable that the two binding sites are directly from the aromatic ring. May also come from different aromatic rings. Further, it is preferable that the carboxyl group or the phenolic hydroxyl group has 1 to 8, and those which are directly bonded to the aromatic ring are also preferable.

In the general formula (I), the monovalent organic group represented by R ³ is preferably an aliphatic group or an aromatic group, more preferably one having 1 to 20 carbon atoms, and an aliphatic hydrocarbon group. Or an aromatic hydrocarbon group is particularly preferred.

The component (a) may have a structural unit other than the repeating unit represented by the general formula (I). For example, the following general formula (III)

Embedded image (Wherein, R ⁶ represents a tetravalent organic group, R ⁷ represents a divalent organic group having no carboxyl group or phenolic hydroxyl group, and R ⁸ represents a monovalent organic group). It may have a repeating unit.

In the general formula (III), 4 represented by R ⁶
The description of the valent organic group is the same as that of R ¹ . In the general formula (III), the description of the divalent organic group having no carboxyl group and no phenolic hydroxyl group represented by R ⁷ means that neither the carboxyl group nor the phenolic hydroxyl group in the above description of R ² Except for R ²
The description is the same as that described above. Further, in the general formula (III), the description of the monovalent organic group represented by R ⁸ is the same as that of R ³ .

In the component (a), one or more of two R ³ or two R ^{8 in} the general formula (I) or (III) may be replaced by a hydrogen atom as another structural unit. May have repeating units. (A)
In the component, the ratio of the repeating units of the general formulas (I) and (III) is m / (m + n) where the former number is m and the latter number is n, and is 0.2 to 1. And more preferably 0.4 to 1. If this value is less than 0.2, the solubility 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 (III), that is, the carboxyl group in the tetracarboxylic acid residue is completely esterified. The total number of repeating units is 50% to 100% of the total number of repeating units.
%, More preferably 80% to 100%, and 90%
-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 the component (a) is preferably from 3,000 to 200,000 in terms of weight average molecular weight.
00 to 100,000 is more preferable. Molecular weight is measured by gel permeation chromatography,
The value can be obtained by conversion using a standard polystyrene calibration curve. In the general formulas (I) and (III), there are two groups represented by R ³ and R ⁸ in each repeating unit, but these may be the same or different. In a plurality of repeating units, R ¹ , R ² , R ³ ,
The groups represented by R ⁶ , R ⁷ and R ⁸ may be the same or different.

In the present invention, the component (a) includes, for example,
Tetracarboxylic diester dihalide (chloride,
Bromide, etc.), a diamine compound having a carboxyl group or a phenolic hydroxyl group, and, if necessary, a diamine compound having no carboxyl group or a phenolic hydroxyl group. in this case,
The reaction is preferably performed in an organic solvent in the presence of a dehaloacid catalyst.

As the tetracarboxylic diester dihalide, tetracarboxylic diester dichloride is preferred. The tetracarboxylic diester dichloride can be obtained by reacting a tetracarboxylic diester obtained by reacting a tetracarboxylic dianhydride with an alcohol compound and thionyl chloride.

The tetracarboxylic dianhydride includes:
For example, pyromellitic dianhydride, 3,3 ', 4,4'-
Biphenyltetracarboxylic dianhydride, 2,3,3 ',
4'-biphenyltetracarboxylic dianhydride, 2,
2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride Anhydride, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,2,2
3,4-cyclopentanetetracarboxylic 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, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3 Aromatic tetracarboxylic diacids such as 3,3 ', 4,4'-tetraphenylsilanetetracarboxylic dianhydride and 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride Are preferred, and these can be used alone or in combination of two or more.

As the alcohol compound, for example,
Methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-
Butyl alcohol, tert-butyl alcohol, isobutyl alcohol, 1-pentanol, 2-pentanol,
Alkyl alcohols such as 3-pentanol, isoamyl alcohol, 1-hexanol, 2-hexanol, and 3-hexanol, phenol, and benzyl alcohol are preferred, and these can be used alone or in combination of two or more.

Examples of the diamine having a carboxyl group or a phenolic hydroxyl group include, for example, 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, and 2,5-diaminoterephthalic acid. , Bis (4-amino-3-carboxyphenyl) methylene, bis (4-amino-3-carboxyphenyl) ether,
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) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-
Hydroxyphenyl) sulfone, bis (3-amino-4)
Aromatic diamine compounds such as -hydroxyphenyl) hexafluoropropane and bis (4-amino-3-hydroxyphenyl) hexafluoropropane are preferred, and these are used alone or in combination of two or more.

Examples of the diamine having no carboxyl group or phenolic hydroxyl group include 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone,
4'-diaminodiphenyl sulfide, benzine, m
-Phenylenediamine, p-phenylenediamine, 1,
5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone,
Bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- (4
-Aminophenoxy) phenyl] ether and aromatic diamine compounds such as 1,4-bis (4-aminophenoxy) benzene are preferable, and these can be used alone or in combination of two or more.

As a diamine having neither a carboxyl group nor a phenolic hydroxyl group, a diamine having the following general formula (IV) for improving adhesion and the like:

Embedded image (Wherein, R ⁹ represents a divalent organic group, R ¹⁰ represents a monovalent organic group, and q is an integer of 1 or more), and a diamine compound having a siloxane bond can be used. . The divalent organic group represented by R ^9, preferably one carbon atoms of 1 to 10, wherein the alkylene group of carbon atoms, be mentioned as a phenylene group or the like, the two R ⁹ are identical It may be different. As the monovalent organic group represented by R ¹⁰ , an organic group having 1 to 6 carbon atoms is preferable, an alkyl group or a phenyl group having the above carbon number is preferable, and four R ¹⁰ may be the same or different. . Further, q is preferably 1 to 70.

The diamine compound represented by the general formula (IV) includes, for example,

Embedded image And the like.

As a commercially available product, when R ⁹ is a trimethylene group and R ¹⁰ is a methyl group in the general formula (IV), q is 1; About 20, about 30 on average, and about 50 on average, LP-7100, X-7
-22-161AS, X-22-161A, X-22
161B, X-22-161C and X-22-161E
(All manufactured by Shin-Etsu Chemical Co., Ltd., trade names) are preferred. When these are used in combination, they are preferably used in an amount of 1 to 30 mol%, more preferably in a range of 3 to 20 mol%, based on the total amount of the diamine compound.

Other diamines having no carboxyl group or phenolic hydroxyl group include 4,4'-diaminodiphenylether-3-sulfonamide and 3,4'-diaminodiphenylether for improving heat resistance.
4-sulfonamide, 3,4'-diaminodiphenylether-3'-sulfonamide, 3,3'-diaminodiphenylether-4-sulfonamide, 4,4'-diaminodiphenylether-3-carboxamide, 3,
Diamine compounds having a sulfonamide group or a carboxamide group such as 4'-diaminodiphenyl ether-4-carboxamide, 3,4'-diaminodiphenyl ether-3'-carboxamide, and 3,3'-diaminodiphenyl ether-4-carboxamide alone or Two or more of them can be used in combination, and when they are used in combination, they are preferably used in an amount of 15 mol% or less, more preferably 10 mol% or less, based on the total amount of the diamine compound.

A method for synthesizing the tetracarboxylic acid diester compound is known. For example, the tetracarboxylic dianhydride and an excess of the alcohol compound are mixed,
After heating and reacting, it is obtained by removing excess alcohol compounds. The ratio (molar ratio) of the tetracarboxylic dianhydride to the alcohol compound is 1 in the former / the latter.
/ 2 to 1/20, preferably 1 / 2.5
More preferably, it is in the range of 1/10. The reaction temperature is preferably 30 to 130 ° C, and the reaction time is preferably 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 ratio (molar ratio) of the tetracarboxylic acid diester and the excess thionyl chloride is preferably in the range of 1/2 to 1/10 in the former / latter, and in the range of 1 / 2.2 to 1/5. Is more preferred. The reaction temperature is preferably from 0 to 100 ° C, and the reaction time is preferably from 1 to 10 hours.

The polyamide acid ester as the component (a) is prepared by, for example, dissolving the diamine compound and a dehalogenating catalyst such as pyridine in an organic solvent, and reacting by dropping a tetracarboxylic diester dihalide dissolved in the organic solvent. After
It is obtained by pouring into a poor solvent such as water, filtering and drying the precipitate. The ratio (molar ratio) of the total amount of the diamine compound and the tetracarboxylic diester dihalide is the former /
In the latter, the range of 0.95 / 1 to 1 / 0.95 is preferable,
The range of 0.98 / 1 to 1 / 0.98 is more preferable. The reaction temperature is preferably −30 to 40 ° C., and the reaction time is 1 to 1
0 hours is preferred. The ratio of the dehaloacid catalyst to the tetracarboxylic diester dihalide is the former / the latter (molar ratio)
Is preferably in the range of 0.95 / 1 to 1 / 0.95,
The range of 98/1 to 1 / 0.98 is more preferred.

When a diamine compound having no carboxyl group or phenolic hydroxyl group is used in combination, the ratio of the diamine compound having a carboxyl group or a phenolic hydroxyl group to the diamine compound having no carboxyl group or a phenolic hydroxyl group is 20 to 100, which is the former. It is preferably used such that the total is 100 mol% with the latter being 80 to 0 mol%, the former being 40 to 100 mol%, and the latter being 6 mol%.
More preferably, it is used so that the total amount is from 0 to 0 mol% to 100 mol%. The former diamine compound is used for imparting solubility to an aqueous alkali solution to the polyamic acid ester, but if it is less than 20 mol%, the sensitivity tends to decrease and the development time tends to be long.

The component (b) used in the present invention, o-
The quinonediazide compound is a photosensitizer, and can be obtained, for example, by subjecting o-quinonediazidosulfonyl chlorides to a hydroxy compound, an amino compound and the like in the presence of a dehydrochlorination catalyst in a condensation reaction. Examples of the 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.

As the hydroxy compound, for example,
Hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane,
2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxy Benzophenone, 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,
10-dimethylindeno [2,1-a] indene, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane and the like can be used.

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 can be used.

The o-quinonediazidosulfonyl chloride and the hydroxy compound and / or the amino compound are 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. Preferably. The preferred ratio between the dehydrochlorination catalyst and o-quinonediazide sulfonyl chloride is 0.95.
/ 1 to 1 / 0.95. The preferred reaction temperature is 0 to 40 ° C, and the preferred reaction time is 1 to 10 hours.

As the reaction solvent, a solvent 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 heat-resistant photosensitive polymer composition of the present invention, the amount of the component (b) is determined based on the difference in dissolution rate between the exposed and unexposed portions and the allowable range of sensitivity. The amount is preferably 5 to 100 parts by weight, more preferably 10 to 40 parts by weight with respect to parts by weight.

The component (c) used in the present invention is a photosensitizer, and the alkyl group of R ⁴ and R ⁵ in formula (II) preferably has 1 to 10 carbon atoms. Specifically, 2,6-dimethyl-3,5-dicarboxymethyl-
4- (2'-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-dicarboxyethyl-4- (2'-nitrophenyl) -1,4-dihydropyridine, 2,6- Dimethyl-3-carboxymethyl-5
-Carboxyisobutyl-4- (2'-nitrophenyl) -1,4-dihydropyridine and the like are preferred. The component (c) includes a residual film ratio of an unexposed portion,
From the viewpoint of the allowable range of sensitivity, it is preferable to add 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the component (a).

The heat-resistant photosensitive polymer composition of the present invention can be obtained by dissolving the components (a), (b), (c) and, if necessary, other components in a solvent. As the solvent, for example, N-methyl-2-pyrrolidone,
Aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, tetramethylene sulfone, and γ-butyrolactone are preferred, and these may be used alone or in combination of two or more. Used.

The heat-resistant photosensitive polymer composition of the present invention comprises:
Further, if necessary, an organic silane compound or an aluminum chelate compound can be contained as an adhesion aid. 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. When using an adhesion aid, component (a) 100
0.1 to 20 parts by weight, preferably 1 to 20 parts by weight,
10 parts by weight is more preferred.

The heat-resistant photosensitive polymer composition of the present invention can be formed into a polyimide relief pattern through a step of coating and drying on a supporting substrate, a step of exposing, a step of developing and a step of heating. . In the step of coating on a supporting substrate and drying, the heat-resistant photosensitive polymer composition is coated on a supporting substrate such as a glass substrate, a semiconductor, a metal oxide insulator (eg, TiO ₂ , SiO ₂ ), or silicon nitride. After spin coating using a spinner or the like, drying is performed using a hot plate, an oven, or the like.

Next, in the exposure step, the photosensitive polymer composition coated on the supporting substrate is irradiated with actinic rays such as ultraviolet rays, visible rays and radiation through a mask. In the developing step, a relief pattern is obtained by removing the exposed portion with a developing solution. Preferred examples of the developer include aqueous alkali solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine and tetramethylammonium hydroxide. The base concentration of these aqueous solutions is 0.
The content is preferably 1 to 10% by weight. Further, an alcohol or a surfactant may be added to the above-mentioned developer for use. Each of these may be added in an amount of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the developer.

Next, in the heat treatment step, the obtained relief pattern is preferably subjected to a heat treatment at 150 to 450 ° C. to form a heat-resistant polyimide relief pattern having an imide ring or another cyclic group.

[0044]

The present invention will be described below with reference to examples. Example 1 In a 0.5 liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, 31.02 g of 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride was placed.
(0.1 mol), n-butyl alcohol 59.30 g
(0.8 mol) was stirred and reacted at 95 ° C. for 5 hours. Excess n-butyl alcohol was distilled off under reduced pressure to obtain 3,3 ', 4,4'-biphenylethertetracarboxylic acid di-n-butyl ester.

Then, thionyl chloride was placed in a flask.
17 g (0.8 mol) and 70.00 g of toluene were charged,
The reaction was performed at 40 ° C. for 3 hours. Excess thionyl chloride was azeotroped with toluene under reduced pressure and removed. 154 g of N-methylpyrrolidone was added to obtain a solution (α) of 3,3 ′, 4,4′-biphenylethertetracarboxylic acid di-n-butyl ester dichloride.

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 10.65 g (0.07 mol) of 3,5-diaminobenzoic acid was added. 4.00 g (0.02 mol) of 4,4'-diaminodiphenyl ether and 2.49 g (0.01 mol) of a silicone diamine compound (LP7100, manufactured by Shin-Etsu Chemical Co., Ltd.) were added, and the mixture was stirred and dissolved. .82 g and the temperature was reduced from 0 to
While maintaining the temperature at 5 ° C., a solution (α) of 3,3 ′, 4,4′-biphenylethertetracarboxylic acid di-n-butyl ester dichloride was added dropwise over 1 hour, and then stirring was continued for 1 hour. Pour the solution into 4 liters of water and collect the precipitate,
After washing, it was dried under reduced pressure to obtain polyamic acid n-butyl ester. The weight average molecular weight of the obtained polyamic acid n-butyl ester was 14,000 (a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve. Measuring device; column, manufactured by Hitachi, Ltd.) Two GL-S300MPT-5 (manufactured by Hitachi Chemical Co., Ltd.) connected in series and used, eluent: THF /
DMF = 1/1, flow rate: 1 ml / min, detection wavelength: 310 n
m, and so on. ).

The polyamic acid n-butyl ester 3
0.005 g of a compound obtained by reacting 4,4'-diaminodiphenyl ether with naphthoquinone-1,2-diazido-5-sulfonyl chloride in a molar ratio of 1/2,
2,6-dimethyl-3,5-dicarboxymethyl-4-
1.50 g of (2'-nitrophenyl) -1,4-dihydropyridine was dissolved with stirring in 65.00 g of N-methylpyrrolidone. This solution was filtered under pressure using a Teflon filter having a pore size of 1 μm to obtain a photosensitive polymer composition.

The obtained photosensitive polymer composition was spin-coated on a silicon wafer using a spinner, and dried by heating at 95 ° C. for 3 minutes on a hot plate to obtain a 6 μm coating film. This coating film was exposed at 100 to 500 mJ / cm ² through a mask using PLA (manufactured by Canon Inc.) as an exposure machine. Next, 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. By pattern observation, the appropriate exposure was determined to be 300 mJ / cm ² . The residual film ratio of the unexposed portion was 92%. Incidentally, the remaining film ratio of the unexposed portion is determined by DEKTAK3030 (Sloan
Inc.) and the film thickness before and after development was measured and calculated (the same applies hereinafter). The obtained relief pattern was placed in a nitrogen atmosphere 3
Heat treatment was performed at 50 ° C. for 1 hour to obtain a good polyimide film pattern.

Example 2 In a 0.5 liter flask equipped with a stirrer, thermometer and Dimroth condenser, 35.83 g of 3,3 ', 4,4'-biphenylsulfonetetracarboxylic dianhydride was prepared.
(0.1 mol), n-butyl alcohol 59.30 g
(0.8 mol) was stirred and reacted at 95 ° C. for 5 hours. Excess n-butyl alcohol was distilled off under reduced pressure to obtain 3,3 ', 4,4'-biphenylsulfonetetracarboxylic acid di-n-butyl ester. Next, 95.17 g (0.8 mol) 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. 154 g of N-methylpyrrolidone was added, and a solution of 3,3 ', 4,4'-biphenylsulfonetetracarboxylic acid di-n-butyl ester dichloride (β)
I got

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 3,5-diaminobenzoic acid 1
0.65 g (0.07 mol), 4.00 g (0.02 mol) of 4,4′-diaminodiphenyl ether, and 2.49 g (0.01 mol) of a silicone diamine compound (LP7100, manufactured by Shin-Etsu Chemical Co., Ltd.) After stirring and dissolving, 15.82 g of pyridine was added, and the temperature was reduced to 0 to 5.
While maintaining the temperature at ° C, a solution (β) of 3,3 ', 4,4'-biphenylsulfonetetracarboxylic 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 polyamic acid n-butyl ester. The weight average molecular weight of the obtained polyamic acid n-butyl ester was 23,000.

This polyamic acid n-butyl ester 3
0.005 g of a compound obtained by reacting 4,4′-diaminodiphenyl sulfone with naphthoquinone-1,2-diazide-5-sulfonyl chloride in a molar ratio of 1/2,
2,6-dimethyl-3,5-dicarboxymethyl-4-
1.50 g of (2'-nitrophenyl) -1,4-dihydropyridine was dissolved with stirring in 65.00 g of N-methylpyrrolidone. This solution was filtered under pressure using a Teflon filter having a pore size of 1 μm to obtain a photosensitive polymer composition.

The obtained photosensitive polymer composition was spin-coated on a silicon wafer using a spinner, and dried by heating on a hot plate at 100 ° C. for 3 minutes to obtain a 6 μm coating film. Using a PLA (manufactured by Canon Inc.) as an exposure machine, 100 to 500 mJ / cm ²
Was exposed. Next, paddle development was performed for 60 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. By pattern observation, proper exposure is 300 mJ / cm ²
It was determined. The residual film ratio of the unexposed portion was 93%. The obtained relief pattern was heated at 350 ° C. for 1 hour under a nitrogen atmosphere to obtain a polyimide film pattern.

Comparative Example 1 n-Butyl ester of polyamic acid 3 obtained in Example 1
0.00g, 7.50 g of a compound obtained by reacting 4,4'-diaminodiphenyl ether with naphthoquinone-1,2-diazido-5-sulfonyl chloride in a molar ratio of 1/2.
Was dissolved in 65.00 g of N-methylpyrrolidone with stirring. This solution was filtered under pressure using a Teflon filter having a pore size of 1 μm to obtain a photosensitive polymer composition. The obtained photosensitive polymer composition was spin-coated on a silicon wafer using a spinner, and dried by heating at 80 ° C. for 3 minutes on a hot plate to obtain a 6 μm coating film. This coating film was exposed at 100 to 500 mJ / cm ² through a mask using PLA (manufactured by Canon Inc.) as an exposure machine. Next, 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. By pattern observation,
The appropriate exposure was determined to be 250 mJ / cm ² . The unexposed portion residual film ratio was 84%.

Comparative Example 2 n-Butyl ester of polyamic acid 3 obtained in Example 1
0.00g, 2,50-dimethyl-3,5-dicarboxymethyl-4- (2'-nitrophenyl) -1,4-dihydropyridine 1.50 g, N-methylpyrrolidone 6
The mixture was stirred and dissolved in 5.00 g. This solution was filtered under pressure using a Teflon filter having a pore size of 1 μm to obtain a photosensitive polymer composition. The obtained photosensitive polymer composition was spin-coated on a silicon wafer using a spinner, and dried by heating at 80 ° C. for 3 minutes on a hot plate to obtain a 6 μm coating film. This coating film was exposed at 100 to 500 mJ / cm ² through a mask using PLA (manufactured by Canon Inc.) as an exposure machine. Subsequently, paddle development was performed for 70 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution, and washing was performed with pure water, but all unexposed portions were dissolved. When the developing time was 40 seconds, a relief pattern was obtained. Appropriate exposure dose is 400mJ by pattern observation
/ cm ² . The unexposed portion residual film ratio was 48%.

[0055]

The heat-resistant photosensitive polymer composition according to claim 1 has high sensitivity and a high residual film ratio in an unexposed area. According to the method for producing a relief pattern according to claim 2, the sensitivity is high,
Since a relief pattern having a high unexposed portion residual film ratio can be provided, it can be used as a surface protective film, an interlayer insulating film, and the like of a semiconductor element.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/075 511 G03F 7/075 511 7/40 501 7/40 501 H01L 21/027 H01L 21/312 B 21/312 21 / 30 502R (72) Inventor Mamoru Sasaki 4-3-1-1, Higashicho, Hitachi City, Ibaraki Pref. Hitachi Chemical Co., Ltd., Semiconductor & Liquid Crystal Materials Division Development Center (72) Inventor Shigeru Nishio 4-chome Higashimachi, Hitachi City, Ibaraki Prefecture 13-1 Hitachi Chemical Co., Ltd. Semiconductor & Liquid Crystal Materials Division Development Center

Claims (2)

[Claims] (A) General formula (I) (Wherein, R ¹ represents a tetravalent organic group, R ² represents a divalent organic group having a carboxyl group or a phenolic hydroxyl group, and R ³ represents a monovalent organic group). A polyamic acid ester having a unit, (b) an o-quinonediazide compound and (c) a general formula (II) (Wherein, R ⁴ and R ⁵ each represent an alkyl group). 2. A step of applying and drying the heat-resistant photosensitive polymer composition according to claim 1 on a support substrate,
A method for producing a relief pattern including a developing step and a heat treatment step.