JPH11100501A - Preparation of positive photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which can be developed with an environmentally friendly alkaline aqueous solution and has an excellent resolution by adding a naphthoquinone diazide compound to a resin obtained by reacting an addition product of a diamine compound having a specific structure and trimellitic anhydride with a hydroxydiamine compound having a specific structure in the presence of a condensing agent in a polar organic solvent. SOLUTION: 5-100 pts.wt. of a naphthoquinone diazide compound is added to 100 pts.wt. of a resin obtained by reacting one time mole of an addition product of one time mole of a diamine compound of formula I (R<1> is a 6-30C divalent organic group), e.g. 4,4-diaminodiphenylether and 1.0-2.5 times mole of trimellitic anhydride with 0.9-1.1 times mole of a hydroxydiamine compound of formula II (R<2> is a 6-30C trivalent to tetravalent organic group; and 1 is 1 or 2) in the presence of a condensing agent (e.g.: 1,1-carbonyldiimidazole) in a polar organic solvent (e.g.: N,N-dimethylacetamide).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive resin composition useful as a surface protective film for semiconductors, and more particularly to a positive photosensitive resin composition which can be developed with an environmentally friendly aqueous developer. And a method for producing the same.

[0002]

2. Description of the Related Art As a positive-type heat-resistant resin composition in which an exposed portion is dissolved by development, a resin obtained by adding naphthoquinonediazide to polyamic acid (for example, JP-A-52-1)
No. 3315), a solution obtained by adding a naphthoquinonediazide to a soluble polyimide having a hydroxyl group (for example, Japanese Unexamined Patent Publication No.
No. 4-60630), a polyamide obtained by adding naphthoquinonediazide to a polyamide having a hydroxyl group (for example, Japanese Patent Application Laid-Open No.
No. 6-27140) is known.

However, in the case where naphthoquinonediazide is added to ordinary polyamic acid, the desired pattern can be obtained in most cases because the dissolution effect of the carboxyl group of polyamic acid is higher than the dissolution inhibiting effect of naphthoquinonediazide in an alkaline developer. There was a problem that it was not possible. In addition, in the case of adding a naphthoquinonediazide to a soluble polyimide resin having a hydroxyl group, although the above-mentioned problems are reduced, the structure is limited in order to make it soluble, and the solvent resistance of the obtained polyimide resin is poor. Points were problems.
Also in the case of adding a naphthoquinonediazide to a polyamide resin having a hydroxyl group, there is a problem that the structure is limited in order to obtain solubility, and the resin obtained after heat treatment is inferior in solvent resistance. Further, the thermally cured film has a drawback that it does not dissolve in strong acids such as fuming nitric acid and concentrated nitric acid, and it has been difficult to perform a defect inspection of a semiconductor.

In view of the above drawbacks, the present invention is to add a naphthoquinonediazide to a novel hydroxyl-containing resin so that the resulting resin composition hardly dissolves in an alkaline developer before exposure and becomes alkaline after exposure. The inventors have found that the film is easily dissolved in a developing solution, and that the thermally cured film is resistant to an organic solvent such as N-methyl-2-pyrrolidone, and is soluble in a strong acid such as fuming nitric acid. Things.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, and provides a positive photosensitive resin composition which can be developed with an environment-friendly alkaline developing solution and has excellent solvent resistance after heat treatment. It is an object of the present invention to provide a method of manufacturing the same.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
With respect to 1 mol of the diamine compound represented by the following general formula (1) and 1 mol of the addition reaction product of 1.0 to 2.5 mol of the trimellitic anhydride, the compound is represented by the following general formula (2). Positive photosensitive resin composition characterized in that a naphthoquinonediazide compound is added to a resin obtained by reacting 0.9 to 1.1 mol of a hydroxydiamine compound in a polar organic solvent in the presence of a condensing agent. Is achieved.

[0007]

Embedded image (R ¹ in the formula represents a divalent organic group having 6 to 30 carbon atoms.)

Embedded image (In the formula, R ² is a trivalent or tetravalent organic group having 6 to 30 carbon atoms, l
Represents an integer of 1 or 2. )

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The resin obtained by the present invention is:
A resin characterized by forming an imide ring or an oxazole ring by heating or an appropriate catalyst. By forming a ring structure, heat resistance and solvent resistance are dramatically improved.

In the general formula (1), R ¹ represents a structural component of a diamine compound. The diamine compound has an aromatic group, and is preferably a divalent organic group having 6 to 30 carbon atoms. Specific examples thereof include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone,
4'-diaminodiphenyl sulfide, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, benzidine, 3,3'-dimethylbenzidine, 3, 3′-dimethoxybenzidine, o-tolidine, 4,4 ″ -diaminoterphenyl, 1,5-diaminonaphthalene, 2,5-diaminopyridine, 3,3′-
Dimethyl-4,4'-diaminodiphenylmethane, 4,
4'-bis (p-aminophenoxy) biphenyl, 2,
Examples include 2-bis [4- (p-aminophenoxy) phenyl] propane, bis [4- (p-aminophenoxy) phenyl] sulfone, hexahydro-4,7-methanoindanylene dimethylene diamine, and particularly, It is not limited to. Further, a part of these aromatic rings may be substituted with an alkyl group, chloro, fluoro, trifluoromethyl group or the like.

Further, it can be modified with another diamine compound in the range of 1 to 40 mol%. Preferred examples include aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and the like. When such a diamine component is copolymerized in an amount of 40 mol% or more, the heat resistance of the obtained resin decreases.

Further, in order to improve the adhesiveness to the substrate, it can be modified with a diamine compound having a siloxane structure as long as the heat resistance is not reduced. Preferred examples include those obtained by copolymerizing bis (3-aminopropyl) tetramethyldisiloxane with 1 to 40 mol%.

In the general formula (2), R ² represents a structural component of a hydroxydiamine compound, and 1 is an integer of 1 or 2. The hydroxydiamine compound has an aromatic group, and is preferably a trivalent to tetravalent organic group having 6 to 30 carbon atoms. As a specific example, 2,2-bis (3-amino-4-
Hydroxyphenyl) hexafluoropropane, 3,
3'-dihydroxy-4,4'-diaminobiphenyl,
3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 4,4'-dihydroxy-3,3'-diaminodiphenylsulfone, 2,2-bis (p-amino-
m-hydroxyphenyl) hexafluoropropane,
3,3'-diamino-4,4'-dihydroxybiphenyl, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diaminophenol and the like can be mentioned.

Diamine compound 1 represented by general formula (1)
The amount of trimellitic anhydride is 1 to 2.5 times, more preferably 1.8 to 2.1 times, and still more preferably 1.95 to 2.05 times the mole of the trimellitic anhydride. An addition reaction is obtained. When the amount of trimellitic anhydride is less than 1 mol, the resin film-forming property becomes insufficient, and many cracks are likely to occur when developing for pattern formation. On the other hand, when the amount of trimellitic anhydride is more than 2.5 moles, the strength of the film obtained from the resin is undesirably small.

The reaction solvent is preferably a polar organic solvent. For example, N, N-dimethylacetamide, N, N-
Dimethylformamide, N-methyl-2-pyrrolidone,
Dimethyl sulfoxide, hexamethylphosphamide, and the like are preferable, and a solvent such as benzene, toluene, xylene, dioxane, and cresol may coexist.

The hydroxydiamine compound represented by the general formula (2) is used in an amount of 0.1 mol per mol of the above-mentioned addition reaction product.
It is preferable to use 9 to 1.1 times mol. More preferably 0.95 to 1.05 moles, even more preferably 0.9 to 1 mole.
It is 9 to 1.01 times mol.

The amount of the condensing agent to be used is preferably 2 to 5 times, more preferably 3.5 to 4.5 times, per mole of the above-mentioned addition reaction product. If the amount of the condensing agent is less than 2 moles, a film having a low strength is obtained, and a good pattern cannot be formed. On the other hand, if the amount of the condensing agent is more than 5 moles, the reaction becomes milky and it becomes extremely difficult to filter insolubles. Furthermore, even after reprecipitation in water or methanol, the filterability of the resin is poor, and the workability is significantly reduced.

As the condensing agent, carbodiimide and the like can be used. For example, 1,1′-carbonyldiimidazole, dicyclohexylcarbodiimide, N, N′-diisopropylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide and the like can be preferably used, and 1H-benzotriazole-1 -Yloxytripyrrolidinophosphonium hexafluorophosphate, N-ethoxycarbonyl-2-ethoxy-1,
2-Dihydroquinoline, diphenylphosphate azide and the like can also be used.

It is preferable to use an equimolar amount or more of an active esterification reagent together with the above condensing agent. This can increase the reaction rate and reduce side reactions.
Preferred active esterification reagents include 1-hydroxybenzotriazole, N-hydroxy-5-norbornene-2,3-dicarboximide, N-hydroxysuccinimide, and 3,4-dihydro-3-hydroxy-4-.
Oxo-1,2,3-benzotriazine and the like can be mentioned. The resin used in the present invention may be used alone, or may be a copolymer or a blend with another structural unit. In that case, it is preferable that the resin produced by the present invention contains 90 mol% or more.
It is preferable to select the type and amount of the structural unit used for the copolymer or the blend within a range that does not impair the heat resistance of the resin obtained by the final heat treatment.

The positive photosensitive resin composition of the present invention contains 5 to 100 parts by weight of a naphthoquinonediazide compound based on 100 parts by weight of the resin. Preferably 10 to 50 parts by weight,
More preferably, it contains 15 to 30 parts by weight. If the naphthoquinonediazide compound is less than 5 parts by weight, it is difficult to obtain a difference in dissolution rate between the exposed part and the unexposed part in the alkaline developer, and if it exceeds 100 parts by weight, the heat resistance of the film after heat curing and mechanical Properties and adhesion are easily impaired.

The naphthoquinonediazide compound to be added in the present invention is preferably a compound in which a sulfonyl acid of naphthoquinonediazide is bonded to a phenolic hydroxyl group by an ester. Examples of such a substance include those represented by the following chemical formulas, but are not limited thereto.

[0021]

Embedded image In addition, compounds such as ethylene glycol or glycerin having an alcoholic hydroxyl group and a compound in which sulfonyl acid of naphthoquinonediazide is ester-bonded, amino groups having an amino group such as aniline, phenylenediamine, diaminodiphenylether, diaminodiphenylmethane and naphthoquinonediazide. The compound having an amide bond of sulfonylic acid, the amino group of a compound having a hydroxyl group and an amino group such as hydroxy-diaminopyrimidine, hydroxydiaminobenzene, aminophenol, bis (hydroxy-aminophenyl) hexafluoropropane, and the sulfonyl acid of naphthoquinonediazide are Amide-bonded compounds, compounds in which the hydroxyl group of these compounds and the sulfonylic acid of naphthoquinonediazide are ester-bonded, Sulfonyl acid both naphthoquinone diazide hydroxyl groups may be used an amide bond and an ester linked compounds.

When the molecular weight of these naphthoquinonediazide compounds exceeds 1200, the naphthoquinonediazide compounds do not thermally decompose sufficiently in the subsequent heat treatment, so that the heat resistance, mechanical properties and adhesion of the resulting film are reduced. May occur. From such a viewpoint, the preferable molecular weight of the naphthoquinonediazide compound is 300 to 1200. More preferably, 35
0 to 1100.

The photosensitive resin composition of the present invention is dissolved in a solvent and used in the form of a varnish. As the solvent, N-
Methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphamide,
Polar solvents such as γ-butyrolactone are commonly used.
In addition to these polar solvents, other common organic solvents such as ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons can be used in combination. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane, dichloromethane, 1, 2-dichloroethane, 1,4
-Dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like can be used. If necessary, a surfactant, ethyl lactate or propylene glycol monomethyl ether acetate may be used for the purpose of improving the wettability between the photosensitive resin composition of the present invention and the substrate.
Esters such as thiol, alcohols such as ethanol,
Ketones such as cyclohexanone and methyl isobutyl ketone and ethers such as tetrahydrofuran and dioxane may be mixed. In addition, inorganic particles such as silicon dioxide and titanium dioxide, or powder of polyimide can also be added.

Further, in order to enhance the adhesion to an underlying substrate such as a silicon wafer, a silane coupling agent such as methylmethacryloxydimethoxysilane and 3-aminopropyltrimethoxysilane, a titanium chelating agent, an aluminum chelating agent and the like are used. The varnish of the conductive resin composition may be added in an amount of 0.5 to 10% by weight, or the underlying substrate may be pretreated with such a chemical. When pre-treating the substrate, the coupling agent described above is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate from 0.5. 20
The solution in which the weight% is dissolved is subjected to surface treatment by spin coating, dipping, spray coating, steam treatment, or the like. In some cases, the reaction between the substrate and the above-mentioned coupling agent can be advanced by applying a temperature of 50 ° C. to 300 ° C. thereafter.

Next, a method for forming a heat-resistant resin pattern using the positive photosensitive resin composition of the present invention will be described.

A varnish of the positive photosensitive resin composition of the present invention is applied on a substrate. The substrate is a silicon wafer,
Ceramics, gallium arsenide, and the like are used, but are not limited thereto. Examples of the coating method include spin coating using a spinner, spray coating, and roll coating. The thickness of the coating varies depending on the coating method, the solid concentration of the composition, the viscosity, and the like, but the coating is usually applied so that the thickness after drying is 0.1 to 150 μm.

Next, the substrate coated with the photosensitive resin composition is dried to obtain a film of the photosensitive resin composition. Drying is o
It is preferable to perform the heat treatment at 50 ° C. to 150 ° C. for 1 minute to several hours using a bun, hot plate, infrared ray or the like.

Next, the film of the photosensitive resin composition is irradiated with actinic radiation through a mask having a desired pattern.
Expose. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. In the present invention, i-line (365 nm), h-line (405 nm), and g-line (4
36 nm).

The formation of the pattern is achieved by removing the exposed portion using a developer after exposure. As a developer, tetramethylammonium hydroxide, ethanolamine, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylamino An aqueous solution of an alkaline compound such as ethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, or hexamethylenediamine is preferred. By adding a small amount of an acid such as acetic acid, boric acid, oxalic acid, or carbonic acid, the alkaline developer can be given a buffering property to suppress the influence of carbon dioxide in the atmosphere during development. In some cases, these alkaline aqueous solutions may contain N-methyl-2-pyrrolidone, N, N
Polar solvents such as dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphonamide and γ-butyrolactone; alcohols such as methanol, ethanol and isopropanol; lactic acid Ester such as ethyl and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be added alone or in combination of several kinds. After the development, the film is rinsed with water. Also in this case, ethanol,
Alcohols such as isopropyl alcohol, ethyl lactate, propylene glycol monomethyl ether acetate
Rinsing treatment may be performed by adding esters and the like to the water.

After development, the film is converted into a heat-resistant resin film by applying a temperature of 200 ° C. to 500 ° C. This heat treatment may be performed by selecting a temperature and raising the temperature stepwise, or may be performed by selecting a certain temperature range and continuously raising the temperature, and is preferably performed for 5 minutes to 5 hours. Examples of these are 130 ° C, 200 ° C,
A method of performing heat treatment at 350 ° C. for 30 minutes each, a method of linearly increasing the temperature from room temperature to 400 ° C. over 2 hours, and the like can be given.

The heat-resistant resin film formed by the photosensitive heat-resistant precursor composition according to the present invention is used for a passivation film of a semiconductor, a protective film of a semiconductor element, an interlayer insulating film of a multilayer wiring for high-density mounting, and the like. Used.

[0032]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to embodiments.

Measurement method of properties Measurement of film thickness The film thickness of the photosensitive resin composition was measured at a refractive index of 1.64 using an optical film thickness measuring device Lambda-ace STM-602 manufactured by Dainippon Screen Co., Ltd. did. When the difference between the film thickness before development (T1) and the film thickness (T2) of the unexposed portion after development was 1.5 μm or more, the contrast between the exposed portion and the unexposed portion was determined to be poor.

Measurement of Viscosity The viscosity was measured at 25 ± 1 ° C. using an EHD type viscometer manufactured by Tokimec.

Example 1 Under dry nitrogen flow, 4.00 g (0.02 mol) of 4,4'-diaminodiphenyl ether and 1.24 g (0.004 g) of bis (3-aminopropyl) tetramethyldisiloxane
5 mol) was dissolved in 100 g of γ-butyrolactone.
9.61 g (0.05 mol) of trimellitic anhydride was added while maintaining the temperature of the solution at 20 ° C.
Allowed to react for hours.

The solution was cooled to 3 ° C., and 13.51 g of 1-hydroxybenzotriazole (HOBt) (0.1
Mol) and completely dissolved, and then a solution of 20.63 g (0.1 mol) of dicyclohexylcarbodiimide dissolved in 50 g of γ-butyrolactone was added dropwise over 30 minutes while maintaining the internal temperature at 5 ° C or lower. Next, a solution obtained by dissolving 9.16 g (0.025 mol) of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane in 100 g of γ-butyrolactone was added dropwise over 30 minutes, and 3 ° C. For 1 hour and at 50 ° C. for 2 hours.

After completion of the reaction, the precipitated urea compound was removed by filtration. The filtrate was poured into 5 liters of a 1% by weight aqueous acetic acid solution to form a resin precipitate. The precipitate was collected, washed with water and methanol, and dried in a vacuum dryer at 50 ° C. for 24 hours.

10 g of this resin, 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinone-
2 g of a naphthoquinonediazide compound (4NT-300, manufactured by Toyo Gosei Co., Ltd.), which is a triester of 2-diazo-5-sulfonylic acid, was dissolved in 30 g of γ-butyrolactone to obtain a varnish A of a positive photosensitive resin composition. . The viscosity of this varnish A was 1.5 Pa · s.

A varnish A is applied on a 6-inch silicon wafer so that the film thickness after prebaking is 4 μm.
Then hot plate (SKW- made by Dainippon Screen Co., Ltd.)
636), and pre-baked at 100 ° C. for 3 minutes.
Exposure machine (Nikon g-line stepper-NSR-1505-
g6E), a reticle having an evaluation pattern of 200 to 1 μm was set, and an exposure amount of 200 mJ / cm ² (43
G-ray exposure at an intensity of 6 nm).

The development was performed using SCW manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a −636 developing device, a 2.4% aqueous solution of tetramethylammonium was sprayed at 50 rpm for 10 seconds. Next, after leaving still for 90 seconds at 0 rotation, it was rinsed with water at 400 rotations, shaken off at 3000 rotations for 10 seconds, and dried. The film thickness of the unexposed portion after the development was 3.4 μm, and the reduction of the film by the development was as small as 0.6 μm, which was good.

As a result of observing the pattern after development,
The pattern of 3 μm required as a semiconductor buffer coat was resolved, and the pattern shape was not a problem.

Example 2 Bis [4- (p-aminophenoxy) in a stream of dry nitrogen
10.81 g (0.025 mol) of [phenyl] sulfone was dissolved in 100 g of γ-butyrolactone. 8. While maintaining the temperature of the solution at 20 ° C., trimellitic anhydride
61 g (0.05 mol) was added and reacted at 20 ° C. for 5 hours.

The solution was cooled to 3 ° C., and 10.13 g of 1-hydroxybenzotriazole (HOBt) (0.03 g) was added.
75 mol), and after completely dissolving, 15.47 g (0.075 mol) of dicyclohexylcarbodiimide was added to γ.
-A solution dissolved in 50 g of butyrolactone was added dropwise over 30 minutes while maintaining the internal temperature at 5 ° C or lower. Then, 2,
A solution obtained by dissolving 9.16 g (0.025 mol) of 2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane in 100 g of γ-butyrolactone was added dropwise over 30 minutes, and added at 3 ° C. for 1 hour. The reaction was performed at 50 ° C. for 2 hours.

After completion of the reaction, the precipitated urea compound was removed by filtration. The filtrate was poured into 5 liters of a 1% by weight aqueous acetic acid solution to form a resin precipitate. The precipitate was collected, washed with water and methanol, and dried in a vacuum dryer at 50 ° C. for 24 hours.

10 g of this resin, 2 g of naphthoquinonediazide compound 4NT-300 (manufactured by Toyo Gosei Co., Ltd.) and 0.1 g of γ-aminopropyltrimethoxysilane
Dissolved in 30 g of butyrolactone to obtain a varnish B of a positive photosensitive resin composition. The viscosity of the varnish B is as follows:
It was 8 Pa · s.

A varnish B was applied on a 6-inch silicon wafer so that the film thickness after prebaking was 4 μm.
Then hot plate (SKW- made by Dainippon Screen Co., Ltd.)
636), and pre-baked at 100 ° C. for 3 minutes.
Exposure machine (Nikon g-line stepper-NSR-1505-
g6E), a reticle having an evaluation pattern of 200 to 1 μm was set, and an exposure amount of 200 mJ / cm ² (36
I-ray exposure at an intensity of 5 nm).

Development was carried out by SCW manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a −636 developing device, a 2.4% aqueous solution of tetramethylammonium was sprayed at 50 rpm for 10 seconds. Next, after leaving still at 0 rotation for 180 seconds, it was rinsed with water at 400 rotations, shaken off at 3000 rotations for 10 seconds, and dried. The film thickness of the unexposed portion after development is 3.2 μm,
The reduction of the film due to development was as small as 0.8 μm, which was good.

As a result of observing the pattern after development,
The pattern of 3 μm required as a semiconductor buffer coat was resolved, and the pattern shape was not a problem.

Example 3 Bis [4- (p-aminophenoxy) in a stream of dry nitrogen
10.81 g (0.025 mol) of [phenyl] sulfone was dissolved in 100 g of γ-butyrolactone. 3. While maintaining the temperature of the solution at 20 ° C, trimellitic anhydride
8 g (0.025 mol) was added and reacted at 20 ° C. for 5 hours.

The solution was cooled to 3 ° C., and 6.76 g (0.05%) of 1-hydroxybenzotriazole (HOBt) was added.
Mol) and completely dissolved, and a solution of 10.32 g (0.05 mol) of dicyclohexylcarbodiimide dissolved in 50 g of γ-butyrolactone was added dropwise over 30 minutes while maintaining the internal temperature at 5 ° C or lower. Then, 2,2'-
A solution prepared by dissolving 8.42 g (0.023 mol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane in 100 g of γ-butyrolactone was added dropwise over 30 minutes, and added dropwise at 3 ° C. for 1 hour and at 50 ° C. The reaction was performed for 2 hours.

After completion of the reaction, the precipitated urea compound was removed by filtration. The filtrate was poured into 5 liters of a 1% by weight aqueous acetic acid solution to form a resin precipitate. The precipitate was collected, washed with water and methanol, and dried in a vacuum dryer at 50 ° C. for 24 hours.

10 g of this resin, 2 g of naphthoquinonediazide compound 4NT-300 (manufactured by Toyo Gosei Co., Ltd.) and 0.1 g of γ-aminopropyltrimethoxysilane
-Dissolved in 30 g of butyrolactone to obtain a varnish C of a positive photosensitive resin composition. The viscosity of the varnish C is 2.
It was 0 Pa · s.

A varnish C was applied on a 6-inch silicon wafer so that the film thickness after prebaking was 4 μm.
Then hot plate (SKW- made by Dainippon Screen Co., Ltd.)
636), and pre-baked at 100 ° C. for 3 minutes.
Exposure machine (Nikon i-line stepper-NSR-1755-
In i7A), a reticle having an evaluation pattern of 200 to 1 μm was set, and an exposure amount of 200 mJ / cm ² (36
I-ray exposure at an intensity of 5 nm).

The development was performed using SCW manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a −636 developing device, a 2.4% aqueous solution of tetramethylammonium was sprayed at 50 rpm for 10 seconds. Next, after leaving still for 90 seconds at 0 rotation, it was rinsed with water at 400 rotations, shaken off at 3000 rotations for 10 seconds, and dried. The film thickness of the unexposed portion after the development was 2.9 μm, and the reduction of the film due to the development was 1.1 μm, which was good.

As a result of observing the pattern after development,
The pattern of 3 μm required as a semiconductor buffer coat was resolved, and the pattern shape was not a problem.

Example 4 5 g (0.025 mol) of 4,4′-diaminodiphenyl ether was added to γ-butyrolactone 100 under a stream of dry nitrogen.
g. 9.61 g (0.05 mol) of trimellitic anhydride while maintaining the temperature of this solution at 20 ° C.
And reacted at 20 ° C. for 5 hours.

After cooling the solution to 3 ° C., 20.63 g (0.1 mol) of dicyclohexylcarbodiimide was added to γ.
-A solution dissolved in 50 g of butyrolactone was added dropwise over 30 minutes while maintaining the internal temperature at 5 ° C or lower. Then, 2,
A solution obtained by dissolving 9.16 g (0.025 mol) of 2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane in 100 g of γ-butyrolactone was added dropwise over 30 minutes, and added at 3 ° C. for 1 hour. The reaction was performed at 50 ° C. for 2 hours.

After completion of the reaction, the precipitated urea compound was removed by filtration. The filtrate was poured into 5 liters of a 1% by weight aqueous acetic acid solution to form a resin precipitate. The precipitate was collected, washed with water and methanol, and dried in a vacuum dryer at 50 ° C. for 24 hours.

10 g of this resin, 2 g of a naphthoquinonediazide compound 4NT-300 (manufactured by Toyo Gosei Co., Ltd.) and 0.1 g of γ-aminopropyltrimethoxysilane
-Dissolved in 30 g of butyrolactone to obtain a varnish D of a positive photosensitive resin composition. The viscosity of the varnish D is 2.
It was 0 Pa · s.

A varnish D is applied on a 6-inch silicon wafer so that the film thickness after prebaking is 4 μm.
Then hot plate (SKW- made by Dainippon Screen Co., Ltd.)
636), and pre-baked at 100 ° C. for 3 minutes.
Exposure machine (Nikon i-line stepper-NSR-1755-
In i7A), a reticle having an evaluation pattern of 200 to 1 μm was set, and an exposure amount of 200 mJ / cm ² (43
G-ray exposure at an intensity of 6 nm).

The development was performed using SCW manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a −636 developing device, a 2.4% aqueous solution of tetramethylammonium was sprayed at 50 rpm for 10 seconds. Next, after leaving still at 0 rotation for 180 seconds, it was rinsed with water at 400 rotations, shaken off at 3000 rotations for 10 seconds, and dried. The film thickness of the unexposed portion after development is 3.1 μm,
The decrease in the film due to development was as small as 0.9 μm, which was good.

As a result of observing the pattern after development,
The pattern of 3 μm required as a semiconductor buffer coat was resolved, and the pattern shape was not a problem.

Comparative Example 1 Under dry nitrogen flow, 5.00 g (0.025 mol) of 4,4'-diaminodiphenyl ether was dissolved in 100 g of γ-butyrolactone. While maintaining the temperature of this solution at 20 ° C., 3.84 g (0.02 mol) of trimellitic anhydride was added and reacted at 20 ° C. for 5 hours.

The solution was cooled to 3 ° C., and 6.76 g (0.05%) of 1-hydroxybenzotriazole (HOBt) was added.
Mol) and completely dissolved, and a solution of 10.32 g (0.05 mol) of dicyclohexylcarbodiimide dissolved in 50 g of γ-butyrolactone was added dropwise over 30 minutes while maintaining the internal temperature at 5 ° C or lower. Then, 2,2'-
A solution prepared by dissolving 7.32 g (0.02 mol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane in 100 g of γ-butyrolactone was added dropwise over 30 minutes, and added dropwise at 3 ° C. for 1 hour and at 50 ° C. The reaction was performed for 2 hours.

After completion of the reaction, the precipitated urea compound was removed by filtration. The filtrate was poured into 5 liters of a 1% by weight aqueous acetic acid solution to form a resin precipitate. The precipitate was collected, washed with water and methanol, and dried in a vacuum dryer at 50 ° C. for 24 hours.

10 g of this resin and 2 g of the naphthoquinonediazide compound 4NT-300 (manufactured by Toyo Gosei Co., Ltd.) were dissolved in 30 g of γ-butyrolactone to obtain a varnish E of a positive photosensitive resin composition. The viscosity of this varnish E is 0.5P
a · s.

A varnish E was applied on a 6-inch silicon wafer so that the film thickness after prebaking was 4 μm.
Then hot plate (SKW- made by Dainippon Screen Co., Ltd.)
636), and pre-baked at 100 ° C. for 3 minutes.
Exposure machine (Nikon g-line stepper-NSR-1505-
g6E), a reticle having an evaluation pattern of 200 to 1 μm was set, and an exposure amount of 200 mJ / cm ² (43
G-ray exposure at an intensity of 6 nm).

The development was performed using SCW manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a −636 developing device, a 2.4% aqueous solution of tetramethylammonium was sprayed at 50 rpm for 10 seconds. Then, after standing still at 0 rotation for 30 seconds, rinsing treatment with water at 400 rotations and shaking off and drying at 3000 rotations for 10 seconds, all films on the wafer were dissolved and no pattern could be obtained.

COMPARATIVE EXAMPLE 2 4 g (0.02 mol) of 4,4'-diaminodiphenyl ether and bis (3-aminopropyl) were mixed in a stream of dry nitrogen.
1.24 g (0.005 mol) of tetramethyldisiloxane was dissolved in 100 g of γ-butyrolactone. While maintaining the temperature of the solution at 20 ° C., 14.41 g (0.075 mol) of trimellitic anhydride was added.
Allowed to react for hours.

The solution was cooled to 3 ° C. and 13.51 g of 1-hydroxybenzotriazole (HOBt) (0.15 g) was added.
Mol) and completely dissolved, and then a solution of 20.63 g (0.1 mol) of dicyclohexylcarbodiimide dissolved in 50 g of γ-butyrolactone was added dropwise over 30 minutes while maintaining the internal temperature at 5 ° C or lower. Next, a solution obtained by dissolving 9.16 g (0.025 mol) of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane in 100 g of γ-butyrolactone was added dropwise over 30 minutes, and 3 ° C. For 1 hour and at 50 ° C. for 2 hours.

After the completion of the reaction, the precipitated urea compound was removed by filtration. The filtrate was poured into 5 liters of a 1% by weight aqueous acetic acid solution to form a resin precipitate. The precipitate was collected, washed with water and methanol, and dried in a vacuum dryer at 50 ° C. for 24 hours.

10 g of this resin and 2 g of a naphthoquinonediazide compound 4NT-300 (manufactured by Toyo Gosei Co., Ltd.) were dissolved in 30 g of γ-butyrolactone to obtain a varnish F of a positive photosensitive resin composition. The viscosity of this varnish F is 1.2P
a · s.

A varnish F was applied on a 6-inch silicon wafer so that the film thickness after prebaking was 4 μm.
Then hot plate (SKW- made by Dainippon Screen Co., Ltd.)
636), and pre-baked at 100 ° C. for 3 minutes.
Exposure machine (Nikon g-line stepper-NSR-1505-
g6E), a reticle having an evaluation pattern of 200 to 1 μm was set, and an exposure amount of 200 mJ / cm ² (43
G-ray exposure at an intensity of 6 nm).

The development was performed using SCW manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a −636 developing device, a 2.4% aqueous solution of tetramethylammonium was sprayed at 50 rpm for 10 seconds. Next, after leaving still for 30 seconds at 0 rotation, it was rinsed with water at 400 rotations, shaken off at 3000 rotations for 10 seconds, and dried. The film thickness of the unexposed portion after the development was 1.7 μm, and the decrease in the film due to the development was as large as 2.3 μm, which was poor.

In addition, many fine cracks were observed in the film after development, and there was a problem in practical use.

Comparative Example 3 Bis [4- (p-aminophenoxy) in a stream of dry nitrogen
10.81 g (0.025 mol) of [phenyl] sulfone was dissolved in 100 g of γ-butyrolactone. 8. While maintaining the temperature of the solution at 20 ° C., trimellitic anhydride
61 g (0.05 mol) was added and reacted at 20 ° C. for 5 hours.

The solution was cooled to 3 ° C., and 13.51 g of 1-hydroxybenzotriazole (HOBt) (0.1%) was added.
Mol) and completely dissolved, and then a solution of 20.63 g (0.1 mol) of dicyclohexylcarbodiimide dissolved in 50 g of γ-butyrolactone was added dropwise over 30 minutes while maintaining the internal temperature at 5 ° C or lower. Next, a solution obtained by dissolving 10.99 g (0.03 mol) of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane in 100 g of γ-butyrolactone was added dropwise over 30 minutes, and 3 ° C. For 1 hour and at 50 ° C. for 2 hours.

After completion of the reaction, the precipitated urea compound was removed by filtration. The filtrate was poured into 5 liters of a 1% by weight aqueous acetic acid solution to form a resin precipitate. The precipitate was collected, washed with water and methanol, and dried in a vacuum dryer at 50 ° C. for 24 hours.

10 g of this resin, 2 g of naphthoquinonediazide compound 4NT-300 (manufactured by Toyo Gosei Co., Ltd.) and 0.1 g of γ-aminopropyltrimethoxysilane
Dissolved in 30 g of butyrolactone to obtain a varnish G of a positive photosensitive resin composition. The varnish G has a viscosity of 0.1.
It was 9 Pa · s.

A varnish G is applied on a 6-inch silicon wafer so that the film thickness after prebaking is 4 μm.
Then hot plate (SKW- made by Dainippon Screen Co., Ltd.)
636), and pre-baked at 100 ° C. for 3 minutes.
Exposure machine (Nikon i-line stepper-NSR-1755-
In i7A), a reticle having an evaluation pattern of 200 to 1 μm was set, and an exposure amount of 200 mJ / cm ² (36
I-ray exposure at an intensity of 5 nm).

The development was performed using SCW manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a −636 developing device, a 2.4% aqueous solution of tetramethylammonium was sprayed at 50 rpm for 10 seconds. Next, after leaving still for 90 seconds at 0 rotation, it was rinsed with water at 400 rotations, shaken off at 3000 rotations for 10 seconds, and dried. The film thickness of the unexposed portion after development was 2.1 μm, and the decrease in the film due to development was as large as 1.9 μm, which was poor.

In addition, many fine cracks were observed in the film after development, and there was a problem in practical use.

[0083]

According to the present invention, it is possible to obtain a positive-type photosensitive composition which can be developed with an environment-friendly aqueous alkaline solution and has excellent resolution.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C08G 69/32 C08G 73/10 73/10 H01L 21/30 502R

Claims (4)

[Claims] 1. A compound represented by the following general formula (1): 1 mol of a diamine compound represented by the following general formula (1) and 1 mol of an addition reaction product of 1.0 to 2.5 mol of trimellitic anhydride are added. A naphthoquinonediazide compound is added to a resin obtained by reacting 0.9 to 1.1 times the molar amount of the hydroxydiamine compound represented by 2) in a polar organic solvent in the presence of a condensing agent; For producing a photosensitive resin composition of a type. Embedded image (R ¹ in the formula represents a divalent organic group having 6 to 30 carbon atoms.) (In the formula, R ² is a trivalent or tetravalent organic group having 6 to 30 carbon atoms, l
Represents an integer of 1 or 2. ) 2. The method for producing a positive photosensitive resin composition according to claim 1, wherein the condensing agent is carbodiimide. 3. The method for producing a positive photosensitive resin composition according to claim 2, wherein the carbodiimide is used in the presence of an active esterification reagent in an equimolar amount or more. 4. The process for producing a positive photosensitive resin composition according to claim 2, wherein the condensing agent is used in an amount of 2 to 5 times the mole of the addition reaction product.