JP2003241371A - Photosensitive resin composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition comprising a polyimide precursor which lowers the coefficient of thermal expansion in imidation, developable with an aqueous alkali solution and having sharp negative pattern forming ability. <P>SOLUTION: The photosensitive resin composition comprises (A) a polyimide precursor of formula (1) (where R<SP>1</SP>and R<SP>2</SP>are each an aromatic organic group; R<SP>3</SP>and R<SP>4</SP>are each an aromatic organic group; R<SP>5</SP>and R<SP>6</SP>are each an organic group having an ethylenically unsaturated bond; and R<SP>7</SP>and R<SP>8</SP>are each an organic group having an α,β-unsaturated bond), (B) a dehydration condensing agent for production of the polyimide precursor, (C) a photosensitive agent to an actinic ray and (D) a solvent. A method for producing the photosensitive resin composition is provided. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art In recent years, polyimide resins have been developed into electric and electronic fields including semiconductors due to their high heat resistance, chemical resistance, electric insulation, low dielectric constant, etc. , IC, LSI, VLSI are used as interlayer insulating films and surface protection films for chips. However, in the conventional polyimide film pattern forming method, after the polyimide precursor is applied and dried on the wafer, it is necessary to perform pattern etching processing using a photoresist, resulting in an increase in cost. A hydrazine solution, which is a harmful substance, had to be used as a polyimide etching solution.

For this reason, material manufacturers have made attempts to introduce a photosensitive group into a polyimide precursor to enable pattern formation of the polyimide itself, and it has come to a practical stage in some product fields. However, the photosensitive polyimides currently in practical use can be roughly classified into those in which a photosensitive group is introduced into a polyimide precursor by an ionic bond and those in which a photosensitive group is introduced through an ester bond. The sensitivity to ultraviolet rays used in (1) is low (the difference in solubility is low), and the solubility of the resin decreases in the process, resulting in a low process margin. In the latter case, on the other hand, a complicated process is required in the production stage and a polymer having a molecular weight sufficient for practical use cannot be obtained. Furthermore, these resins use a negative pattern formation method,
In pattern formation, development must be performed with an organic solvent, which is a serious problem from the viewpoint of environmental protection.

Further, with the recent increase in the size of wafers, the warp of the wafer due to the thermal shrinkage of polyimide causes the destruction of the element and the reduction of reliability due to the separation of the chip and the sealing material in the subsequent process. It is desired to reduce the coefficient of thermal expansion of polyimide.

Due to these problems, an aqueous alkaline solution can be used for pattern formation, and the developer has a negative-type photosensitivity that does not swell and enables high resolution, and also lowers the coefficient of thermal expansion during imidization. There is a strong demand for polyimide precursors.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to eliminate the above-mentioned drawbacks of the prior art, to provide a negative-type patterning material capable of developing with an aqueous alkaline solution, and to use a polyimide precursor having a low coefficient of thermal expansion. PROBLEM TO BE SOLVED: To provide a stable resin composition and a method for stably producing this polyimide precursor.

[0007]

Means for Solving the Problems As a result of intensive research aimed at achieving the above object, the present inventor has adopted a resin composition having a thermally crosslinkable terminal functional group described below and a method for producing the same. It was found that the above-mentioned object can be achieved by doing so, and the present invention has been completed.

That is, the photosensitive resin composition of the present invention is
(A) a polyimide precursor represented by the following general formula,

[Chemical 3] (However, in the formula, R¹, R²Is a tetravalent aromatic group, a plurality of
A tetravalent organic group with a single aromatic ring bond, or multiple aromatic groups
The group ring is -O-, -CO-, -SO₂-Or-CH₂−
Is a tetravalent organic group bonded by³, R^FourIs divalent
Aromatic group, divalent organic compound in which multiple aromatic rings are single-bonded
A group or a plurality of aromatic rings is -O-, -CO-, -SO₂
-Or-CH₂A divalent aromatic group bonded by-
R^Five, R ⁶Has one or more ethylenically unsaturated bonds
R is a monovalent organic group⁷, R⁸Is the αβ unsaturated
Is an organic group having a bond, and m and n are integers of 1 or more.
Is) (B) Used in manufacturing the above polyimide precursor
Dehydrating and condensing agent, (C) improve sensitivity to actinic rays
It consists of a photosensitizer and (D) solvent used for
To collect.

Further, the method for producing the photosensitive resin composition of the present invention comprises (1) an acid dianhydride having a skeleton of R ¹ and R ^{2 represented} by the general formula of Chemical formula 3 and a skeleton of R ⁵ and R ⁶ . An esterification reaction step with a compound having (2) a diamine compound having a skeleton of R ³ and R ^{4 in} Formula 3 under the addition of a dehydration condensation agent Polycondensation reaction step (3) Reaction of polycondensation reaction product of (2) with acid dianhydride having skeleton of R ¹ and R ² shown in the general formula of Chemical formula (4) General formula of chemical formula 3 Reaction with an acid anhydride having a skeleton of R ⁷ and R ⁸ shown therein (5) a step of purifying a polyimide precursor subjected to polycondensation reaction, and (6) a step of preparing a polyimide precursor solution containing a photosensitizer Is characterized by.

The present invention will be described in detail below.

First, the method for producing the photosensitive resin composition of the present invention will be described in the order of steps (1) to (6), and at the same time, the components (A) to (D) of the photosensitive resin composition of the present invention will be described. explain.

(1) Esterification reaction step of the acid dianhydride having R ¹ and R ² skeletons in the formula of Chemical formula 3 and the compound having R ⁵ and R ⁶ skeletons R ¹ of the polyimide precursor of the present invention, Examples of the acid component having an R ² skeleton include pyromellitic acid, 3,
3 ', 4,4'-biphenyltetracarboxylic acid, 2,
3,3 ', 4'-biphenyltetracarboxylic acid, 3,
3 ', 4,4'-benzophenone tetracarboxylic acid,
4,4'-oxydiphthalic acid, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,3,6,7- Naphthalene tetracarboxylic acid,
1,2,5,6-naphthalene tetracarboxylic acid, 1,
4,5,8-naphthalene tetracarboxylic acid, 1,2,
3,4-cyclobutanetetracarboxylic acid, 1,2,3
4-butanetetracarboxylic acid, 1,2,4,5-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3,3 ', 4,4'-bicyclohexyltetracarboxylic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1,
Examples thereof include 2,3,4-tetrahydronaphthalene-1-succinic acid and anhydrides thereof, and these can be used alone or in combination.

Examples of the compound having an R ⁵ or R ⁶ skeleton to be introduced into the acid component serving as the R ¹ or R ² skeleton by an ester bond include, for example, pentaerythritol triacrylate,
Pentaerythritol trimethacrylate, pentaerythritol acrylate dimethacrylate, pentaerythritol diacrylate methacrylate, glycerol diacrylate, glycerol dimethacrylate, glycerol acrylate methacrylate, 1,3-diacryloylethyl-5-hydroxyethyl isocyanurate, ethylene glycol modified pentatrierythritol Triacrylate, propylene glycol-modified pentatrierythritol triacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, 2-hydroxyethyl acrylate, 2
-Hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate and the like are used, and these are used alone or in combination of two or more. can do. Also,
These can be used in a range of 1.5 to 3.0 times, preferably 2.0 to 2.5 times the mol of the above acid component.

An acid component having the above R ¹ and R ² skeletons and the above R
The esterification reaction of the compound having the R ⁵ and R ⁶ skeletons is performed, for example, by using an acid dianhydride having the R ¹ and R ² skeletons and an alcohol having the R ⁵ and R ⁶ skeletons, and a reaction solvent good for synthesizing a polyimide precursor. It is preferable to carry out the reaction at room temperature in the presence of a basic aprotic polar solvent such as N-methyl-2-pyrrolidone or the like and a basic catalyst such as triethylamine, pyridine or triethanolamine to facilitate the reaction.
This basic catalyst can be used in a range of 1.5 to 3.0 times, preferably 2.0 to 2.5 times the mol of the above acid component.

(2) Polycondensation reaction step of the above ester compound and the diamine compound having the R ³ and R ⁴ skeletons in the above formula 3 As the diamine compound having the R ³ and R ⁴ skeletons used in the present invention, , For example, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,5-
Diaminotoluene, 1-methoxy-2,4-diaminobenzene, 1,4-diamino-2-methoxy-5-methylbenzene, 1,3-diamino-4,6-dimethylbenzene, 1,2-diaminonaphthalene, 1 , 4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8
-Diaminonaphthalene, 2,3-diaminonaphthalene,
2,6-diaminonaphthalene, 1,4-diamino-2-
Methylnaphthalene, 1,5-diamino-2-methylnaphthalene, 1,3-diamino-2-phenylnaphthalene,
2,2-bis (4-aminophenyl) propane, 1,1
-Bis (4-aminophenyl) ethane, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4 '
-Diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane,
3,3'-dimethyl-5,5'-diethyl-4,4'-
Diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 4,
4'-methylenebis (cyclohexylamine), 4,
4'-methylenebis (3,3-dimethyl-cyclohexylamine), 2,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,
3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminobenzanilide, 3,3'-diaminodiphenyl ether,
3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, bis (4-aminophenyl) diethylsilane, bis (4-aminophenyl) diphenylsilane, bis (4-aminophenyl) -N-methylamine, bis (4-Aminophenyl) -N-phenylamine, 3,3'-diaminobenzophenone, 4,4 '
-Diaminobenzophenone, 2,6-diaminopyridine, 3,5-diaminopyridine, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 3,3'-
Dimethyl-4,4'-diaminobiphenyl, 3,3'-
Dimethoxy-4,4'-diaminobiphenyl, 3,3 '
-Dihydroxy-4,4'-diaminobiphenyl, o-
Toluidine sulfone, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-
Aminophenoxy) phenyl] ether, bis [4-
(4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene,
1,3-bis (4-aminophenoxy) benzene, 9,
10-bis (4-aminophenyl) anthracene, 9,
9-bis (4-aminophenyl) fluorene, 2,2-
Bis (4-aminophenyl) hexafluoropropane,
2,2-bis (3-aminophenyl) hexafluoropropane, 1,1-bis (4-aminophenyl) -1-phenyl-2,2,2-trifluoroethane, 2,2-bis (3-amino) -4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2-bis [4
-(4-aminophenoxy) phenyl] hexafluoropropane and the like can be mentioned, and these can be used alone or in combination of two or more kinds. In addition, these compounds are R
¹ , ¹ to 5 times the molar amount of the acid dianhydride as the R ² skeleton is preferably used, but it can be used in the range of 2 to 3 times the molar amount depending on the purpose of use, final viscosity and molecular weight. .

Next, the dehydration condensing agent used in the polycondensation reaction of the above ester compound and diamine component in the present invention will be explained.

When the acid component and the diamine component of the above (1) esterification reaction product are reacted by a polycondensation method, it is usually carried out using an acid chloride, but in the electric and electronic fields including a semiconductor device, Since the released chlorine ion causes poor product reliability, it is necessary to sufficiently wash with pure water after polycondensation when carrying out the polymerization by the acid chloride method. As another polycondensation method, it is possible to use a carbodiimide derivative such as DCC (dicyclohexylcarbodiimide) which is a dehydration condensation agent.
There are problems such as side reactions occurring simultaneously, gelation of the polyimide precursor, and toxicity, and it is difficult to completely remove urea generated as a by-product. Therefore, the reaction system must be cooled, the dehydration condensing agent must be added in several batches, or the molar balance between the acid component and the diamine component must be disrupted before use. In addition, as another method, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazole) phosphonate and its derivative, diphenyl (2,3 -Dihydro-2-thioxo-3-benzothiazole) phosphonate and a derivative thereof, a polycondensation method can be mentioned. Since this method enables stable production under mild conditions, it has high resolution and high film properties. It is possible to obtain a polyimide precursor having These may be used alone or in combination of two or more. These can be used in an amount of 1 to 3 times, preferably 2 to 2.5 times the molar amount of the above ester compound.

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

[0019] (3) R ^1, the polyimide precursor in the reaction the present invention with R ^1, an acid dianhydride having R ² skeleton represented in the repeating units of the polycondensation reaction and of 3 (2) R Examples of the acid component having ^two skeletons include pyromellitic acid, 3,
3 ', 4,4'-biphenyltetracarboxylic acid, 2,
3,3 ', 4'-biphenyltetracarboxylic acid, 3,
3 ', 4,4'-benzophenone tetracarboxylic acid,
4,4'-oxydiphthalic acid, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,3,6,7- Naphthalene tetracarboxylic acid,
1,2,5,6-naphthalene tetracarboxylic acid, 1,
4,5,8-naphthalene tetracarboxylic acid, 1,2,
3,4-cyclobutanetetracarboxylic acid, 1,2,3
4-butanetetracarboxylic acid, 1,2,4,5-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3,3 ', 4,4'-bicyclohexyltetracarboxylic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1,
Examples thereof include 2,3,4-tetrahydronaphthalene-1-succinic acid and anhydrides thereof, and these can be used alone or in combination. In addition, these compounds are
With respect to the diamine component serving as the R ³ and R ⁴ skeletons, the acid dianhydride having the R ¹ and R ² skeletons used in (1) and (3) is 0.
It is preferable to use it so that the molar ratio is 9 to 1 times.

(4) Reaction with an acid anhydride having an R ⁷ or R ⁸ skeleton shown in the repeating unit of Chemical formula 3 Examples of the acid anhydride having an R ⁷ or R ⁸ skeleton include allyl nadic acid anhydride. , Methyl nadic acid anhydride, 1-cyclopentene-1,2-anhydride, 1,2,5,6-tetrahydroxyphthalic anhydride, 3,4,5,6-tetrahydroxyphthalic anhydride, croton An acid anhydride, a methacrylic acid anhydride, an allyl nadic acid anhydride, a methyl nadic acid anhydride, an alkenyl nadic acid anhydride, a maleic acid anhydride, etc. are used, and these may be used alone or in combination of two or more. it can. In addition, these compounds are
0.01 to dianhydride having R ¹ and R ² skeleton
It can be used in a 0.1-fold molar range, preferably in a 0.03-0.05-fold molar range.

(5) Step of Purifying Polycondensation Precursor of Polyimide Precursor The obtained slurry polymer is methanol, ethanol,
After stirring and washing in a poor solvent such as isopropyl alcohol or water, the deposited product is dried under reduced pressure to obtain the compound having the resin skeleton represented by the above chemical formula 3.

(6) Process for preparing a solvent containing a photopolymerization initiator, a sensitizer, a storage stabilizer, and a photosensitizer. Further, in the present invention, a photoreaction initiator or a photoinitiator is added for the purpose of improving sensitivity and resolution. A solvent containing a sensitizer or a photosensitizer may be added.

Examples of the photoreaction initiator include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, 2,2'-diethoxyacetophenone and 2-hydroxy-2. -Acetophenone derivatives such as methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, thioxanthone, 2-methylthioxanthone, 2-
Isopropyl thioxanthone, diethyl thioxanthone, benzyl, benzyl dimethyl ketal, benzoin, benzoin methyl ether, 2,6'-di (4'-
Diazidobenzal) -4-ethylcyclohexanone,
Azide compounds such as 2,6′-di (4′-diazidobenzal) -4-butylcyclohexanone and 2,6′-di (4′-diazidobenzal) -4- (t-butyl) cyclohexanone, 1-phenyl-1, 2-butadion-2-
(O-Methoxycarbonyl) oxime, 1-phenyl-
Propanedion-2- (o-methoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2-
(O-Ethoxycarbonyl) oxime, 1-phenyl-
Oximes such as 3-ethoxy-propanetrione-2- (o-benzoyl) oxime, N-phenylglycine,
Examples thereof include glycine derivatives such as N- (p-ethyl) phenylglycine and N- (p-methyl) phenylglycine, and these may be used alone or in combination of two or more. The addition amount of these is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the composition.

The photoreaction initiator used in the present invention is an i ray (365 nm) or g ray (436n) in ultraviolet rays.
The compound is not limited to the above compounds as long as it can efficiently generate a reactive radical in m).

As the sensitizer used in the present invention, for example, Michler's ketone, 4,4'-bis (diethylaminobenzophenone), 2,5-bis (diethylaminobenzal) cyclopentanone, 2,6-bis ( 4'-diethylaminobenzal) cyclohexanone, 2,6-bis (4'-dimethylaminobenzal) -4-methylcyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4, 4'-bis (diethylamino) chalcone, 4,4'-bis (dimethylamino) chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, 2- (p-dimethylaminophenylbiphenylene)- Benzothiazole, 2- (p-dimethylaminophenylvinylene)- Nzochiazoru, 1,3-bis (4'-dimethylamino benzal) acetone, 3,3 '
-Carbonyl-bis (7-diethylaminocoumarin),
3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin,
3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethanolamine, N-phenylethanolamine, NP-tolyldiethanolamine, N-phenylmethanolamine, 4 -Morphoninobenzophenone dimethylaminoisoamyl benzoate,
2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole,
1-Phenyl-5-mercapto-1H-tetrazole and the like can be mentioned, and these can be used alone or in combination of two or more kinds. The amount of addition is 100
0.1 to 10 parts by weight is preferable with respect to parts by weight. Also,
By using these sensitizers according to the wavelength to be used and further according to the required sensitivity, the resolution at each wavelength can be improved.

As the polymerization inhibitor for improving the storage stability of the resin, hydroquinone derivatives such as hydroquinone, methylhydroquinone and butylquinone can be used. These compounds can be used alone or in combination of two or more. The addition amount is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin composition.

The resin composition obtained by the present invention is used in the form of being dissolved in a solvent. Examples of the solvent used for the dissolution include N-methylpyrrolidone,
Aprotic polar solvents such as N, N'-dimethylacetamide, N, N'-dimethylformamide, cyclohexanone, cyclopentanone, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, Examples thereof include butyl lactate and γ-butyrolactone, which can be used alone or in combination of two or more.

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

When considering application to a semiconductor device, first, the resin composition is coated on a target wafer using a spin coater, and then the coating film is dried at 80 to 120 ° C. A mask having a pattern drawn on the obtained coating film is transmitted to irradiate active ultraviolet rays of 365 nm and 436 nm. Next, heat treatment is performed again at 80 to 120 ° C. Next, this coating film is treated with an alkaline aqueous solution, for example, an inorganic alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or ammonia, a primary amine such as ethylamine or n-propylamine, diethylamine or di-n-propyl. Use secondary amines such as amines, tertiary amines such as triethylamine and methyldimethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, and aqueous solutions of quaternary amines such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Then, only the portion not irradiated with actinic rays is dissolved and developed, and rinsed with pure water.
As a developing method, a method such as spraying, paddle, dipping, and ultrasonic wave can be considered. As a result, a desired negative pattern can be obtained on the target wafer.
Furthermore, by heat-treating this coating film, this resin composition can be imidized to form a negative pattern of a polyimide film having excellent film characteristics.

[0030]

In other words, the greatest feature of the present invention is due to the fact that the following negative pattern forming method and the mechanism of lowering the thermal expansion coefficient by thermal crosslinking reaction of terminal unsaturated bonds are discovered. The present resin composition, in the above-mentioned method of use, is subjected to a spin coating drying step on a substrate, and then a radical generator is reacted in an active ray irradiation part by irradiating this coating film with an active ray such as an ultraviolet ray, Radicals are generated.
A compound having an R ⁵ or R ⁶ skeleton chemically reacts with this radical to form a crosslinked structure. By heating in the next step, the reaction of the compound having the R ⁵ and R ⁶ skeletons is promoted. Since this polymer has a carboxyl group, it has a high solubility in an alkaline aqueous solution, but since the compound having the R ⁵ and R ⁶ skeletons forms a crosslinked structure, it becomes insoluble in the alkaline aqueous solution. As a result, only the portion irradiated with an actinic ray such as ultraviolet rays becomes insoluble and does not dissolve, and the unirradiated portion exhibits solubility in an alkaline aqueous solution. Due to this high contrast, the photosensitive resin composition of the present invention can form a negative pattern having high resolution and good dimensional controllability. In the thermosetting reaction after pattern formation,
High crystallinity can be obtained by having a terminal unsaturated bond, so that the coefficient of thermal expansion can be reduced.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below based on Examples.

Example 1 A reaction flask equipped with a nitrogen inlet tube was charged with 0.6 mol of benzophenonetetracarboxylic dianhydride, 2 L of N-methyl-2-pyrrolidone and 1.3 mol of 2-hydroxyethyl methacrylate. And stir for 1.3
Mol triethylamine is added dropwise over 30 minutes. This state was left for 3 hours. Next, 1 mol of metaphenylenediamine was added and stirred for 30 minutes, and then 2.1 mol of diphenyl (2,3-dihydro-2-thioxo-3-benzoxazole) phosphonate was added in 5 batches, and in that state for 5 hours. Conduct a condensation reaction. Next, 0.35 mol of benzophenonetetracarboxylic acid dianhydride is added and stirred for 2 hours, and 0.1 mol of methyl nadic acid anhydride is added and stirred for 2 hours. The reaction solution is poured into a large amount of methanol for reprecipitation, and a large amount of methanol is further added to the obtained slurry mixture for washing, and the obtained solid resin is dried by a vacuum dryer for 12 hours. 30 g of dried solid resin and 0.5 g of N-phenylglycine are added to 70 g.
It was dissolved in g of N-methyl-2-pyrrolidone, and the resulting solution was filtered by 1 μm to obtain Sample 1.

A 6-inch silicon wafer was coated with this sample 1 by using a spin coater, and dried by heating on a baking plate at 90 ° C. for 3 minutes to give a film thickness of 10 μm.
A coating film of This coating film was exposed to 300 mj by an ultraviolet exposure machine using a filter that transmits only 365 nm.
Irradiating the test pattern with energy of / cm ² , followed by heating at 90 ° C. for 1 minute on a baking plate, and then 2.38.
% TMAH (tetramethylammonium hydride) aqueous solution for 1 minute of paddle development. By this operation, it was possible to obtain a negative relief pattern in which the coating film other than the ultraviolet irradiation portion was dissolved. When the obtained pattern was observed with an optical microscope, it was confirmed that a pattern of up to 5.0 μm was sharply formed.

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

Further, the sample 1 obtained was processed into a film and the coefficient of thermal expansion was measured, and the result was 40 ppm, which was lower than that of the conventional product.

Example 2 To a reaction flask equipped with a nitrogen introducing tube, 0.8 mol of biphenyltetracarboxylic dianhydride, 2 L of N-methyl-2-pyrrolidone and 1.7 mol of 2-hydroxyethyl methacrylate were added. And stir, then continue 1.7mo
1 of triethylamine is added dropwise over 30 minutes. This state was left for 3 hours. Next, 1 part of paraphenylenediamine
After adding mol and stirring for 30 minutes, 2.1 mol of diphenyl (2,3-dihydro-2-thioxo-3-benzoxazole) phosphonate is added in 5 batches and the condensation reaction is carried out for 5 hours in that state. Next, 0.18 mol of biphenyltetracarboxylic dianhydride is added and stirred for 2 hours, and then 0.05 mol of allyl nadic acid anhydride is added and stirred for 2 hours. The reaction solution is poured into a large amount of methanol for reprecipitation, and a large amount of methanol is further added to the obtained slurry mixture for washing, and the obtained solid resin is dried by a vacuum dryer for 12 hours. 30 g of dried solid resin and 0.5 g of N-phenylglycine
Was dissolved in 70 g of N-methyl-2-pyrrolidone, and the resulting solution was filtered by 1 μm to obtain Sample 2.

A 6-inch silicon wafer was coated with this sample 2 by using a spin coater, and dried by heating on a baking plate at 85 ° C. for 3 minutes to give a film thickness of 10 μm.
A coating film of This coating film was exposed to 300 mj by an ultraviolet exposure machine using a filter that transmits only 365 nm.
Irradiating the test pattern with energy of / cm ² , followed by heating at 85 ° C. for 1 minute on a baking plate, and then 2.38.
% TMAH (tetramethylammonium hydride) aqueous solution for 90 seconds of paddle development. By this operation, it was possible to obtain a negative relief pattern in which the coating film other than the ultraviolet irradiation portion was dissolved. When the obtained pattern was observed with an optical microscope, it was confirmed that a pattern of up to 5.0 μm was sharply formed.

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

The sample 2 obtained was processed into a film and the coefficient of thermal expansion was measured to be 40 ppm, which was lower than that of the conventional product.

[0040]

INDUSTRIAL APPLICABILITY The present invention is a photosensitive polyimide precursor having a negative pattern forming ability, and an alkaline aqueous solution can be used for pattern formation. Therefore, not only the obtained pattern has less swelling in a developing solution and an extremely sharp high-resolution pattern can be obtained, but also industrial wastes of organic solvents, which have been generated in large quantities up to now, can be completely abolished. In addition, since the finally obtained polyimide coating film has a low coefficient of thermal expansion and is excellent in heat resistance and chemical resistance, it can be used in the same manner as a semiconductor device protective film that is normally used. . The present invention relates to the resin skeleton itself used in the photosensitive resin composition and a method for producing the same, but these are based on a completely new idea, and are extremely excellent inventions that are unique to others. It's easy to understand.

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Claims (2)

[Claims] 1. A polyimide represented by the following general formula:
Precursor, [Chemical 1] (However, in the formula, R¹, R²Is a tetravalent aromatic group, a plurality of
A tetravalent organic group with a single aromatic ring bond, or multiple aromatic groups
The group ring is -O-, -CO-, -SO₂-Or-CH₂−
Is a tetravalent organic group bonded by³, R^FourIs divalent
Aromatic group, divalent organic compound in which multiple aromatic rings are single-bonded
A group or a plurality of aromatic rings is -O-, -CO-, -SO₂
-Or-CH₂A divalent aromatic group bonded by-
R^Five, R ⁶Has one or more ethylenically unsaturated bonds
R is a monovalent organic group⁷, R⁸Is the αβ unsaturated
Is an organic group having a bond, and m and n are integers of 1 or more.
Is) (B) Used in manufacturing the above polyimide precursor
Dehydration condensing agent, (C) Used to improve sensitivity to actinic rays
Photosensitizer and (D) Solvent A photosensitive resin composition comprising: 2. (1) R represented by the following general formula¹as well as
R²Dianhydride having the skeleton of R and R^FiveAnd R⁶The skeleton of
Esterification reaction step with one compound, [Chemical 2] (However, in the formula, R¹, R²Is a tetravalent aromatic group, a plurality of
A tetravalent organic group with a single aromatic ring bond, or multiple aromatic groups
The group ring is -O-, -CO-, -SO₂-Or-CH₂−
Is a tetravalent organic group bonded by³, R^FourIs divalent
Aromatic group, divalent organic compound in which multiple aromatic rings are single-bonded
A group or a plurality of aromatic rings is -O-, -CO-, -SO₂
-Or-CH₂A divalent aromatic group bonded by-
R^Five, R ⁶Has one or more ethylenically unsaturated bonds
R is a monovalent organic group⁷, R⁸Is the αβ unsaturated
Is an organic group having a bond, and m and n are integers of 1 or more.
Is) (2) Esterification of (1) under the addition of dehydration condensing agent
Reactants and R in Formula 2³And R^FourDiamine with skeleton
Polycondensation reaction step with a compound, (3) Polycondensation reaction product of (2) and chemical formula 2
R¹And R²With acid dianhydrides having a skeleton (4) R shown in the general formula of Chemical formula 2⁷And R⁸The skeleton of
Reaction with acid anhydride (5) Purification process of the polycondensed polyimide precursor and
And (6) Step of preparing polyimide precursor solution containing photosensitizer A method for producing a photosensitive resin composition, comprising: