JPH1124270A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive compsn. developable with an alkali which is mild for the environment and showing excellent solvent resistance after heat treatment by incorporating a specified polymer and a quinone diazide compd. SOLUTION: This compsn. contains a polymer expressed by the formula and a quinone diazide compd. In the formula R1 is a tri or quadrivalent org. group having at least two carbon atoms, R2 is a tri to hexavalent org. group having at least two carbon atoms, R3 is a hydrogen atom or 1 to 10C univalent org. group, m is an integer 10 to 100000, m is 1 or 2, p is an integer 1 to 4. The polymer forms imide rings by heating, which improves the heat resistance. R1 in the formula represents the structural component of acid dianhydride, and for example, it is a phenyl group or biphenyl group. R2 has a structural component of the diamine and for example, 2,2-bishexafluoropropane and 3,3'- dihydroxy-4,4'-diaminodiphenyl ether.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition useful as a semiconductor surface protective film, and more particularly to a photosensitive heat-resistant resin precursor composition which can be developed with an environmentally friendly aqueous developer.

[0002]

2. Description of the Related Art As a positive type heat-resistant resin precursor composition in which an exposed portion is dissolved by development, a composition obtained by adding naphthoquinonediazide to polyamic acid (for example, Japanese Patent Application Laid-Open No.
2-13315), a solution obtained by adding naphthoquinonediazide to a soluble polyimide having a hydroxyl group (see, for example,
4-60630), a polyamide obtained by adding naphthoquinonediazide to a polyamide having a hydroxyl group (for example, JP-A-56-2).
7140) are known.

However, in the case of adding naphthoquinonediazide to polyamic acid, the desired pattern cannot be obtained in most cases because the solubility of carboxyl groups of polyamic acid is high due to the dissolution inhibiting effect of naphthoquinonediazide on alkali. There was a problem. In addition, in the case where a soluble polyimide resin having a hydroxyl group is added, the above-mentioned problems are reduced, but the structure is limited in order to make it soluble, and the solvent resistance of the obtained polyimide resin is poor. Met. The addition of naphthoquinonediazide to a polyamide resin having a hydroxyl group also has a limitation in the structure in order to obtain solubility, therefore, the resin obtained after heat treatment is inferior in solvent resistance, and the heat-cured film emits smoke. It has the drawback that it does not dissolve in strong acids such as nitric acid and concentrated sulfuric acid, and it has been difficult to perform a defect inspection of a semiconductor.

In view of the above-mentioned drawbacks, the present inventors have found that by adding naphthoquinonediazide to a polyamic acid ester having a hydroxyl group, the obtained resin composition hardly dissolves in an alkali developing solution before exposure, and The present invention was found to easily dissolve in an alkali developing solution, and found that the thermally cured film was resistant to organic solvents such as N-methyl-2-pyrrolidone and was dissolved by a strong acid such as fuming nitric acid. It has been reached.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, and enables environmentally friendly alkali development.
It is another object of the present invention to provide a photosensitive composition having excellent solvent resistance after heat treatment.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
(A) General formula (1)

Embedded image (Wherein, R ₁ is a trivalent or tetravalent organic group having at least 2 carbon atoms, R ₂ is a tri- to hexavalent organic group having at least 2 carbon atoms, R ₃ is a hydrogen atom or A monovalent organic group having 1 to 10 carbon atoms, and n
Is an integer from 10 to 100000, m is 1 or 2,
p is an integer from 1 to 4. ) And (b) a quinonediazide compound.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer represented by the general formula (1) in the present invention can be a polymer having an imide ring or another cyclic structure by heating or an appropriate catalyst. By having a ring structure, heat resistance and solvent resistance are dramatically improved.

In the general formula (1), R ₁ represents a structural component of an acid dianhydride. The acid dianhydride contains an aromatic ring and has 6 to 30 carbon atoms. Tetravalent groups are preferred. Specifically, a phenyl group, a biphenyl group, a diphenyl sulfone group, a diphenyl ether group, a naphthyl group, a hexafluorodiphenylpropane group, a diphenylpropane group, a bis (phenoxyphenyl) propane group,
Examples include, but are not limited to, benzophenone groups.

In the above general formula (1), R ₂ represents a structural component of a diamine. Among them, preferred examples of R ₂ include 2,2-bis (m-amino-p-hydroxyphenyl) hexafluoropropane, 3,3′-dihydroxy-4,4′-diaminobiphenyl, and 3,3 ′ -Dihydroxy-4,4'-diaminodiphenyl ether, 4,
4'-dihydroxy-3,3'-diaminodiphenylsulfone, hydroxy-metaphenylenediamine, 2,2
-Bis (p-amino-m-hydroxyphenyl) hexafluoropropane, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3-hydroxy-1,5-diaminobenzene, 6-hydroxy-2,4- Examples thereof include diaminopyrimidine, 5,6-diamino-2,4-dihydroxypyrimidine, and 2,4-diamino-6-hydroxytriazine, and more preferably, general formulas (4), (5), and (6). ), But are not limited thereto.

[0010]

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Embedded image In the general formula (4), R ₉ and R ₁₁ are a trivalent to hexavalent organic group having a hydroxyl group having 3 to 20 carbon atoms. From the viewpoint of heat resistance of the obtained resin, it is preferable that the resin contains an aromatic ring and has one or two hydroxyl groups. Further, it is preferable that a hydroxyl group is present at a position adjacent to an amino group or an amide group. R ₁₀ represents a divalent organic group having 2 to 20 carbon atoms. From the viewpoint of the heat resistance of the obtained resin, R
₁₀ preferably has an aromatic ring, phenylene group, diphenyl ether group, diphenylmethane group, diphenylsulfone group, diphenylcarbonyl group, bis (phenyl) hexafluoropropane group, bis (phenyl)
A group such as a propane group can be mentioned as a preferred example. t and u are both integers from 1 to 4.

In the general formula (5), R ₁₂ is a divalent organic group having a hydroxyl group having 3 to 20 carbon atoms, and R ₁₃ is a trivalent organic group having 3 carbon atoms.
A trivalent to hexavalent organic group having 2 to 20 hydroxyl groups, and v is 1
To 4 is an integer. In the general formula (6), R ₁₄ and R
₁₆ is a divalent organic group having a hydroxyl group having 3 to 20 carbon atoms, and R ₁₅ is a divalent organic group having a hydroxyl group having 3 to 20 carbon atoms.
A bivalent to hexavalent organic group, w is an integer of 1 to 4. Such an organic group has an aromatic ring,
It preferably has a heterocyclic ring, and more preferably has a structure represented by chemical formula (7), chemical formula (8) or chemical formula (9).

[0012]

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Embedded image It can also be modified with other diamine components in the range of 1 to 50 mol%. Examples of these include aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, aromatic paraphenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (aminophenoxyphenyl) propane, bis (aminophenoxy) Phenyl) sulfone and the like. If such a diamine component is copolymerized in an amount of 50 mol% or more, the solubility in an alkali developing solution is reduced, so that further copolymerization is not preferable.

Further, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized in R ₁ and R ₂ as long as the heat resistance is not reduced. Specific examples of the diamine component include those obtained by copolymerizing bis (3-aminopropyl) tetramethyldisiloxane with 1 to 10 mol%. R ₃ represents an organic group having 1 to 10 carbon atoms, or And,
It represents a group containing one or more hydrogen atoms. Further, when R ₃ is an organic group having 10 or more carbon atoms, the solubility in an alkali developing solution decreases, and the exposed portion may not be dissolved, which is not preferable.

Preferred examples of R ₃ include a hydrogen atom, a saturated hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group, an ethoxymethyl group and an ethoxy group. Ethyl group,
Groups such as butoxymethyl group, 2-hydroxypropyl group, 2-hydroxypentyl group, 2-hydroxy-3-
It is an organic group having an alcoholic hydroxyl group such as a methoxypropyl group, a 2-hydroxy-3-ethoxypropyl group, and a 2-hydroxy-3-propyloxypropyl group.
In addition, a group such as a hydroxyphenyl group having a phenolic hydroxyl group, a hydroxynaphthyl group, a hexadecyl group having 10 or more carbon atoms, or a lauryl group may be used.
It can be denatured up to mol%. In the present invention, R
₃ may be composed of one type or two or more types.

Further, imide ring closing treatment may be performed for the purpose of controlling the solubility in an aqueous alkali solution. Such imide ring closure treatment is preferably performed in an amount of from 10 to 100%, more preferably from 30 to 70%. Such imide ring closure treatment may be performed by a method using a mixed solution of acetic anhydride and pyridine, a method of polymerizing by applying heat at 50 to 200 ° C., an acid such as amine such as triethylamine, methanesulfonic acid, or gamma. A method using a lactone such as butyrolactone as a catalyst can be used. The imidation ratio in the present invention can be determined by an infrared absorption spectrum method.

The polymer represented by the general formula (1) is
R ₁ , R ₂ , and R ₃ may each be composed of one type, or may be a copolymer composed of two or more types. Further, it may be a copolymer or a blend with another structural unit. Preferred are the polymers represented by the general formulas (2) and (3).

[0017]

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Embedded image R ₄ in the general formula (2) is a divalent organic group containing at least two carbon atoms and represents a dicarboxylic acid residue, and from the viewpoint of the heat resistance of the obtained polymer, those having an aromatic ring Is preferred. Such examples include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, and their alkyl- and halogen-substituted ones.
In addition, it is necessary to use such substances as aliphatic adipic acid and oxalic acid.
It can be modified in an amount of 0 mol% or less. Further, a dicarboxylic acid having a siloxane bond, such as 1,3-bis (3-carboxypropyl) tetramethyldisiloxane, can be used.

R ₅ is a trivalent to hexavalent group having at least 2 carbon atoms, and the same groups as those described above for R ₂ can be used. m is an integer from 10 to 10000,
q is an integer of 1 to 6.

In the general formula (3), R ₆ is at least 2
A trivalent to tetravalent organic group containing carbon atoms, and the same as the above-mentioned R ₁ can be used. R ₇ is a divalent group having at least two carbon atoms and represents a diamine component. In view of the heat resistance of the obtained polymer, a compound having an aromatic ring is preferable. Examples thereof include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone, and the like. further,
Those containing silicon such as aliphatic diamine compounds such as cyclohexyldiamine and methylenebiscyclohexylamine, and 1,3-bis (3-aminopropyl) tetramethyldisiloxane as long as the properties of the film are not significantly changed. Can also be used. The amount of modification of such an aliphatic diamine compound is desirably 40 mol% or less, more desirably 30 mol% or less of the whole diamine component. R ₇ is a trivalent to hexavalent group having at least 2 carbon atoms, and R ₈ is hydrogen or a carbon atom having 1 to 20 carbon atoms.
And r is an integer of 10 to 10000, and s is an integer of 1 to 2.

When the polymer represented by the general formula (2) is used, the polymer represented by the general formula (2) is used in an amount of 10 to 200 parts by weight based on 100 parts by weight of the polymer represented by the general formula (1). Is contained in the photosensitive composition.

When the polymer of the general formula (3) is used, the polymer of the general formula (3) is used in an amount of 1 to 50 parts by weight based on 100 parts by weight of the polymer represented by the general formula (1).
A photosensitive composition containing 5 to 100 parts by weight of a quinonediazide compound.

When copolymerizing or blending a compound having a structure other than those represented by the general formulas (2) and (3),
It is preferable to contain 90 mol% or more of the structural unit represented by the general formula (1). The type and amount of the structural unit used for copolymerization or blending are preferably selected within a range that does not impair the heat resistance of the polyimide-based polymer obtained by the final heat treatment and the solubility in an alkaline developer during pattern processing.

These polyimide precursors are synthesized by a known method. For example, it can be synthesized by the methods described in JP-A-61-72022 and JP-A-55-30207.

As the naphthoquinonediazide compound to be added to the present invention, a compound in which a sulfonyl acid of naphthoquinonediazide is ester-bonded to a phenolic hydroxyl group is preferable. Examples of such a material include, but are not limited to, those shown in chemical formula (10).

[0025]

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 1000, the naphthoquinonediazide compound does 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 1,000. More preferably, 35
0 to 800.

The solvent used in the present invention includes, for example, N-methyl-2-pyrrolidone, gamma-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and the like, which are common solvents for polyamic acid esters. Solvents such as polar aprotic solvents, ethers such as tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone and diisobutyl ketone, esters such as propylene glycol monomethyl ether acetate and ethyl lactate, and aromatic hydrocarbons such as toluene. They can be used alone or as a mixture.

Further, inorganic particles such as silicon dioxide and titanium oxide, or powder of polyimide may be added.

Further, in order to enhance the adhesiveness to an underlying substrate such as a silicon wafer, a silane coupling agent, a titanium chelating agent and the like are added to the varnish of the photosensitive heat-resistant resin precursor composition in an amount of 0.5 to 10% by weight. Alternatively, the underlying substrate can be treated with such a chemical solution in advance.

When added to the varnish, a silane coupling agent such as methylmethacryloxydimethoxysilane and 3-aminopropyltrimethoxysilane, a titanium chelating agent and an aluminum chelating agent are added to the polymer in the varnish in an amount of 0.5 to 10%. % By weight.

When treating the substrate, the above-mentioned coupling agent is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, or the like. The solution in which 5 to 20% by weight is dissolved is subjected to surface treatment by spin coating, dipping, spray coating, steam treatment, or the like. In some cases, then 50 ° C to 300 ° C
The reaction between the substrate and the coupling agent is allowed to proceed by applying a temperature up to and then used.

Next, a method for forming a heat-resistant resin pattern using the photosensitive composition of the present invention will be described. The photosensitive composition of the present invention is applied on a substrate. As the substrate, a silicon wafer, ceramics, gallium arsenide, or the like is used, but is not limited thereto. As a coating method, there are methods such as 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 composition is dried to obtain a photosensitive composition film. Drying is preferably performed using an oven, a hot plate, infrared rays or the like at a temperature of 50 ° to 150 ° for 1 minute to several hours.

Next, the photosensitive composition film is exposed to actinic radiation through a mask having a desired pattern. Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays.
Line (365 nm), h line (405 nm), g line (436
nm). However, 450-
Visible light of 550 nm, ultraviolet light of 350 nm or less, electron beam, X-ray, and the like can also be used.

The formation of the polyimide pattern is achieved by removing the exposed portions using a developing solution after the exposure. As a developing solution, an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylamine An aqueous solution of an alkaline compound such as aminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine is preferred. In some cases, a polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, or dimethylacrylamide, methanol, Alcohols such as ethanol and isopropanol
, Ethyl lactate, esters such as propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone alone or in combination of several kinds. Good. After development, it is rinsed with water. Also in this case, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate and the like may be added to water for rinsing.

After development, the film is converted into a heat-resistant resin film by applying a temperature of 200 to 500 degrees. This heat treatment is carried out for 5 minutes to 5 hours while selecting the temperature and increasing the temperature stepwise, or while selecting a certain temperature range and continuously increasing the temperature. As an example, heat treatment is performed at 130 degrees, 200 degrees, and 350 degrees for 30 minutes each. Alternatively, a method of linearly raising the temperature from room temperature to 400 ° C. over 2 hours may be used.

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

[0038]

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

Measurement method of characteristics Measurement of film thickness The film thickness of the photosensitive resin precursor 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. The film thickness before development (T1)
When the film thickness (T2) of the unexposed portion after development was 1.5 μm or more, it was determined that the contrast between the exposed portion and the unexposed portion was poor.

Measurement of resistance to organic solvent and solubility in fuming nitric acid A 4 inch silicon wafer was spin-coated so that the film thickness after heat treatment at 350 ° C. became 10 μm. This was prebaked on a hot plate (SKW-636 manufactured by Dainippon Screen Co., Ltd.) for 3 minutes at 80 degrees and 3 minutes at 100 degrees. Subsequently, in an inert oven INH-5 manufactured by Koyo Lindberg Co., Ltd., the temperature was raised to 140 ° C. for 30 minutes and then to 350 ° C. over 1 hour at an oxygen concentration of 20 ppm or less, and heat treatment was performed at 350 ° C. for 1 hour. did.

The heat-treated wafer was cut in half, and N-methyl-2-pyrrolidone (NMP) was added on one film at a time.
Oven that has dropped to 200 degrees (Yamato Scientific D
T-42) for 10 minutes. If the solvent resistance is poor,
A phenomenon such as cracking, swelling and dissolution is observed around the area where NMP is dropped. Those having such a phenomenon were regarded as having poor solvent resistance.

The other half was immersed in fuming nitric acid at 80 ° C. for 3 minutes, and visually examined whether or not the film was dissolved. It is preferable to completely dissolve, and when it does not dissolve, it is considered that the solubility to fuming nitric acid is insufficient. When the film remains, a lambda ace STM- manufactured by Dainippon Screen Co., Ltd.
Using 602, the film thickness remaining at a refractive index of 1.77 was measured. Here, there is a problem particularly when the film remains 2 μm or more.

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

Measurement of imidation ratio Dainippon Screen Co., Ltd. was applied to a 4-inch silicon wafer.
Using a coater part of Coater Developer SCW-636, manufactured by Co., Ltd., the film thickness after baking at 50 ° C. for 20 minutes was 7 μm.
m. Then, SCW-63
Baking treatment was performed at 60 ° C. for 20 minutes using the hot plate of No. 6.

[0045] The wafer was subjected to a Fourier transform infrared spectrophotometer FT / IR-5000 manufactured by JASCO Corporation for 1 hour.
The infrared absorption spectrum was measured by integrating six times.

From this spectrum, the intensity of the peak derived from the imide group observed at around 1780 cm ^-1 is measured (I). After that, the same wafer was subjected to 1 hour using an inert oven INH-5 manufactured by Koyo Lindberg Co., Ltd.
The temperature was raised to 350 ° C. for 30 minutes at 40 ° C. and 1 hour,
Heat treatment at 50 ° C. for 1 hour to complete the imidization. The infrared absorption spectrum of this wafer is measured in the same manner as described above, and the intensity of the peak near 1780 cm-1 is measured (I0). The value obtained by multiplying I / I0 by 100 was defined as the imidation ratio.

Measurement of Water Absorption On a 6-inch silicon wafer, a film thickness after heat treatment at 350 ° C. was 15 using a spin coater part of SCW-636.
It was spin-coated to a thickness of μm. This is SCW
Prebaked at 120 ° C. for 4 minutes on a −636 hot plate. The wafer was heated at 140 ° C. for 30 minutes, then heated to 350 ° C. for 1 hour, and heat-treated at 350 ° C. for 1 hour. After completion of the heat treatment, the periphery was damaged and immersed in 47% hydrofluoric acid for 3 minutes to peel off the polyimide film from the silicon wafer. This polyimide film was dried at 200 ° C. for 1 hour using an inert oven DT-42 manufactured by Yamato Scientific. The weight of this film was measured using an electronic balance ER-182A manufactured by A & D (G0). After the measurement was completed, the film was immersed in water at 23 ° C. for 24 hours, and then the water adhering to the film surface was wiped, and the weight was measured (G).

The value obtained by multiplying (G−G0) / G0 by 100 was defined as the water absorption. It is not preferable that the water absorption exceeds 3%.

The structure of the quinonediazide compound used in this example is shown below.

[0050]

Embedded image The structures of the diamine compounds (15) to (19) synthesized in the synthesis examples are shown below.

[0051]

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Synthesis Example 1 Synthesis of diamine compound (15) 2-amino-4-nitrophenol 1 in a stream of dry nitrogen
5.4 g (0.1 mol), 10.1 g of triethylamine
(0.1 mol) was dissolved in 300 ml of acetone. The solution was cooled to 0 ° C. 100 m of acetone in this solution
10.2 g of isophthalic acid dichloride dissolved in
(0.05 mol) was gradually added dropwise so that the temperature of the solution did not exceed 5 ° C. After completion of the dropwise addition, the mixture was stirred at 20 ° C. for 2 hours. After the completion of the reaction, the solution was filtered, and the solvent was removed by an evaporator to obtain a yellow solid. This solid was dissolved in 100 ml of gamma-butyrolactone and 100 ml of ethanol,
Hydrogen was supplied from a balloon with vigorous stirring at room temperature together with 2 g of 5% palladium / carbon to reduce nitro groups to amino groups. The reaction was stopped when hydrogen was no longer absorbed into the system, and the solution was filtered to remove palladium carbon. The filtrate was poured into 1 liter of water to precipitate a brown precipitate, which was collected by filtration. This brown precipitate was recrystallized from a mixed solution of ethanol and gamma-butyrolactone (melting point: 258 ° C.).

Synthesis Example 2 Synthesis of diamine compound (16) 2-amino-4-nitrophenol 1 under a stream of dry nitrogen
5.4 g (0.1 mol) was dissolved in 300 ml of acetone. The solution was cooled to 5 ° C. 4,4′- dissolved in 100 ml of N-methyl-2-pyrrolidone in this solution
12.9 g of dicarboxydiphenyl ether (0.05
Mol) was added. A solution prepared by dissolving 20.6 g of dicyclohexylcarbodiimide (0.1 mol) in 50 g of gamma-butyrolactone was gradually added dropwise so that the temperature of the solution did not exceed 10 ° C. After completion of the dropwise addition, the mixture was stirred at 20 ° C. for 2 hours, 5 g of ethanol was added, and the mixture was further stirred for 2 hours. After the completion of the reaction, the solution was filtered and poured into 3 l of water to obtain a tan precipitate. The precipitate was collected by filtration and air-dried. This solid is mixed with 100 ml of gamma butyrolactone and 100 ml of ethanol.
Then, hydrogen was supplied from a balloon while vigorously stirring at room temperature with 2 g of 5% palladium / carbon to reduce nitro groups to amino groups. The reaction was stopped when hydrogen was no longer absorbed into the system, and the solution was filtered to remove palladium carbon. The filtrate was poured into 1 liter of water to precipitate a brown precipitate,
This was collected by filtration. The brown precipitate was recrystallized from a mixed solution of ethanol and gamma-butyrolactone.

Synthesis Example 3 Synthesis of diamine compound (17) 2-amino-4-nitrophenol 1 under a dry nitrogen stream
5.4 g (0.1 mol) was dissolved in 300 ml of acetone. The solution was cooled to 5 ° C. To this solution was added 19.9 g (0.05 mol) of 2,2-bis (4-carboxydiphenyl) hexafluoropropane dissolved in 200 ml of N-methyl-2-pyrrolidone. Here 20.
6 g of dicyclohexylcarbodiimide (0.1 mol)
Was dissolved in 50 g of gamma-butyrolactone, and the solution was gradually added dropwise so that the temperature of the solution did not exceed 10 ° C. After completion of the dropwise addition, the mixture was stirred at 20 ° C. for 2 hours, 5 g of ethanol was added, and the mixture was further stirred for 2 hours. After the reaction is completed, the liquid is filtered,
It was poured into 3 l of water to obtain a tan precipitate. The precipitate was collected by filtration and air-dried. This solid is treated with gamma butyrolactone 100m
and 2 g of 5% palladium / carbon with vigorous stirring at room temperature while supplying hydrogen from a balloon to reduce nitro groups to amino groups. The reaction was stopped when hydrogen was no longer absorbed into the system, and the solution was filtered to remove palladium carbon. The filtrate was poured into 1 liter of water to precipitate a brown precipitate, which was collected by filtration. The brown precipitate was recrystallized from a mixed solution of ethanol and gamma-butyrolactone.

Synthesis Example 4 Synthesis of diamine compound (18) 2-amino-4-nitrophenol 1 under a stream of dry nitrogen
5.4 g (0.1 mol), triethylamine 11.1 g
(0.11 mol) was dissolved in 100 ml of gamma-butyrolactone. The solution was cooled to 5 ° C. To this solution was added 39.5 g (0.105 mol) of paranitrobenzoyl chloride dissolved in 200 ml of gamma butyrolactone.
It was added dropwise over 0 minutes. After completion of the dropwise addition, the mixture was stirred at 5 ° C. for 3 hours. After the completion of the reaction, the solution was filtered and poured into 3 l of water to obtain a tan precipitate. The precipitate was recrystallized from gamma-butyrolactone. The crystals were dissolved in 400 ml of gamma-butyrolactone, and hydrogen was supplied from a balloon with vigorous stirring at room temperature with 2 g of 5% palladium / carbon to reduce nitro groups to amino groups. The reaction was stopped when hydrogen was no longer absorbed into the system, and the solution was filtered to remove palladium carbon.
The filtrate was poured into 1 liter of water to precipitate a brown precipitate, which was collected by filtration. The brown precipitate was recrystallized from a mixed solution of ethanol and gamma-butyrolactone.

Synthesis Example 5 Synthesis of Diamine Compound (19) 36.6 g (0.1 mol) of BAHF was dissolved in 200 ml of acetone in a 500 ml four-necked flask equipped with a stirring blade, a nitrogen inlet tube, and a thermometer. Cooled to ° C. Glycidyl methyl ether (0.12 mol) was added thereto and stirred.

M-Aminobenzoic acid chloride (0.21 mol) is dissolved in 100 ml of acetone. Put this solution in B
AHF was added dropwise to a solution of acetone and glycidyl methyl ether so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, the temperature was gradually raised from -15 ° C, and 2 hours later, the temperature was raised to 15 ° C, followed by stirring at 15 ° C for 3 hours. Thereafter, the deposited precipitate was collected by filtration. The precipitate is acetone 500m
After washing with 1 l, the mixture was dispersed in 500 ml of hot water at 50 ° C., filtered, and dried in vacuum at 80 ° C. for 20 hours.

After drying, 40 g of the obtained solid was dispersed in 200 ml of gamma-butyrolactone. 4 g of 50% water-containing 5% palladium-carbon (NE Chemcat Co., Ltd., K type) was added thereto, and the mixture was placed in a stainless steel autoclave having a capacity of 300 ml. Keep hydrogen pressure at 8kgf / cm2,
The reduction reaction was performed while stirring at 0 ° C. for 2 hours. After the completion of the reaction, when the temperature of the internal solution became 40 ° C. or lower, the solution was filtered to remove palladium-carbon, and the filtrate was cooled overnight to collect diamine (3) that was crystallized.
For 30 hours (yield 30 g, yield 83%, melting point 31)
8 ° C).

Example 1 Pyromellitic anhydride (PMDA) 1 under a stream of dry nitrogen
0.9 g (0.05 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) 1
6.1 g (0.05 mol) of gamma-butyrolactone (G
BL) dissolved in 200 g. 9.2 g of ethanol (0.2 mol) and 14 g of pyridine were added thereto and reacted at 50 ° C. for 3 hours. The solution was cooled in an ice bath to bring the internal temperature to 5 ° C. A solution in which 41.2 g of dicyclohexylcarbodiimide (0.2 mol) was dissolved in 50 g of GBL was added dropwise over 1 hour. Further, a solution in which 36.6 g (0.1 mol) of 2,2-bis (methamino-parahydroxyphenyl) hexafluoropropane (BAHF) was dissolved in 150 g of GBL was added dropwise over 30 minutes. This solution was reacted for 3 hours under ice cooling, and then reacted at 50 ° C. for 1 hour. After the reaction, the precipitated urea compound was removed by filtration. The filtrate was poured into 5 l of water to produce a polyamic acid ester precipitate. This precipitate was collected, washed with water and methanol, and dried at 50 ° C. for 24 hours in a vacuum drier. 10 g of this polymer and 2 g of a naphthoquinonediazide compound having the chemical structure (11) were dissolved in 30 g of GBL to obtain a varnish A of a photosensitive composition having a viscosity at 25 ° C. of 1 Pa · s. Varnish A of a photosensitive composition was coated on a 6-inch silicon wafer so that the film thickness after prebaking would be 4 μm, and then a hot plate (Dainippon Screen)
The film was prebaked at 100 ° C. for 3 minutes using SCW-636 (manufactured by Toshiba Corporation) to obtain a photosensitive resin composition film. Next, an exposure machine (Nikon i-line stepper-NSR)
-1755-i7A), the reticle on which the pattern was cut was set, and i-ray exposure was performed at an exposure amount of 200 mJ / cm ² (intensity of 365 nm). For development, a 1.5% aqueous solution of tetramethylammonium was sprayed at 50 rpm for 10 seconds using a developing device of SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd. After that, it was left still at 0 rotation for 90 seconds, rinsed with water at 400 rotations, and shake-dried at 3000 rotations for 10 seconds. The thickness of the unexposed portion after development was 3.8 μm.
m, and the film loss of the unexposed portion due to the development was as good as 0.2 μm. Further, as a result of observing the developed pattern after the development, a 5 μm pattern which can sufficiently withstand the requirements as a buffer coat for semiconductors was resolved, and the pattern shape was not a problem.

As a result of an organic solvent resistance test, there was no problem in solubility in fuming nitric acid. The imidation ratio of this varnish is 1
It was 0%. The water absorption was 9%.

Example 2 10.9 g (0.05 mol) of PMDA under a stream of dry nitrogen
And BTDA 16.1 g (0.05 mol) GBL 200 g
Was dissolved. 4.6 g of ethanol (0.1 mol), 1.8 g (0.1 mol) of water, and 14 g of pyridine were added thereto and reacted at 50 ° C. for 3 hours. Here is BAHF2
A solution of 5.6 g (0.07 mol) and 3.2 g of metaphenylenediamine (0.03 mol) in 150 g of GBL was added, and the solution was cooled in an ice bath. When the internal temperature reached 5 ° C., a solution in which 41.2 g of dicyclohexylcarbodiimide (0.2 mol) was dissolved in 50 g of GBL was dropped into this solution over 1 hour. This solution was reacted for 3 hours under ice cooling, and then reacted at 50 ° C. for 1 hour. After the reaction, the precipitated urea compound was removed by filtration. The filtrate was poured into 5 l of water to produce a polymer precipitate. This precipitate was collected, washed with water and methanol, and dried at 50 ° C. for 24 hours in a vacuum drier. This polymer 1
0 g and 2 g of the naphthoquinonediazide compound having the chemical structure (12) are dissolved in 30 g of GBL, and the viscosity at 25 degrees is 1.
Varnish B of a photosensitive composition having a pressure of 2 Pa · s was obtained. Varnish B of a photosensitive composition was coated on a 6-inch silicon wafer so that the film thickness after prebaking was 5 μm, and then a hot plate (SCW-63 manufactured by Dainippon Screen Mfg. Co., Ltd.) was used.
Using 6), prebaking was performed at 100 ° C. for 3 minutes to obtain a photosensitive composition film. Then, the reticle with the pattern cut was set on an exposure machine (Nikon i-line stepper-NSR-1755-i7A), and the exposure amount was 200 mJ / c.
i-ray exposure was performed at m2 (intensity of 365 nm). For development, a 3% diethylaminoethanol aqueous solution was sprayed at 50 rpm for 10 seconds using a developing device of SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd. After that, it was left still for 120 seconds at 0 rotation, sprayed with water for 10 seconds at 400 rotations, and rinsed.
The mixture was shaken off at 3000 rpm for 10 seconds and dried. The film thickness of the unexposed portion after the development was 4.8 μm, and the reduction of the film in the unexposed portion due to the development was as very good as 0.2 μm.
Further, as a result of observing the pattern after development after development, 5 μm which can sufficiently withstand the requirement as a buffer coat for semiconductor was used.
The pattern of m was resolved, and the pattern shape was not a problem.

As a result of an organic solvent resistance test, there was no problem in solubility in fuming nitric acid. The imidation ratio of this varnish is 1
5%. The water absorption was 7%.

Example 3 3,3'-Dihydroxy-4,4'- under a stream of dry nitrogen
15.1 g (0.07 mol) of diaminobiphenyl (HAB), 6.0 g of 4,4'-diaminodiphenyl ether
(0.03 mol) with N-methyl-2-pyrrolidone (NM
P) Dissolved in 150 g at 20 degrees. Here, BTDA
32.2 g (0.1 mol) was added together with 50 g of NMP, and the reaction was carried out at 20 ° C. for 1 hour and then at 50 ° C. for 3 hours. Here, 13.2 g of methyl glycidyl ether
(0.15 mol) together with 20 g of NMP, and reacted at 50 ° C. for 20 hours. 50 g of this solution and the chemical structure (1
2 g of the naphthoquinonediazide compound of 3) was dissolved in 5 g of GBL to obtain a varnish C of a photosensitive composition having a viscosity of 1.3 Pa · s at 25 degrees. 1% on 6 inch silicon wafer
Of isopropyl alcohol solution of 3-aminopropyltriethoxysilane was applied at 2,000 revolutions and treated on a hot plate at 100 ° C. for 1 minute. Here, a varnish C of the photosensitive composition was applied so that the film thickness after prebaking was 5 μm, and then heated to 100 ° C. using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.). For 3 minutes to obtain a photosensitive composition film. Then, an exposure machine (Canon contact aligner PLA)
-501), set the mask with the cut pattern,
Exposure was performed at an exposure dose of 200 mJ / cm2 (intensity of 365 nm). Development was carried out by SCW-63 manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a developing device of No. 6, a 1.2% aqueous solution of tetramethylammonium was sprayed at 50 rpm for 10 seconds. After this, 80
After standing still for 400 seconds, water was sprayed at 400 rotations for 10 seconds to perform a rinsing treatment, and the mixture was shaken off at 3000 rotations for 10 seconds and dried. The film thickness of the unexposed portion after development was 3.8 μm, and the reduction in film thickness of the unexposed portion due to development was as good as 1.2 μm.
Further, as a result of observing the developed pattern after the development, it was found that the pattern as a buffer coat for semiconductors can sufficiently withstand the requirements.
The μm pattern was resolved, and there was no problem with the pattern shape.

The results of the test for resistance to organic solvents were satisfactory, but the treatment with fuming nitric acid left a film of 5000 Å. The imidation ratio of this varnish was 25%. The water absorption was 6%.

Example 4 Under dry nitrogen flow, 10.9 g (0.05 mol) of PMDA and 16.1 g (0.05 mol) of BTDA were added to GBL2.
Was dissolved in 00 g. To this, 13.0 g of 1-octyl alcohol (0.1 mol), 3.2 g of methanol (0.1 mol) and 14 g of pyridine were added and reacted at 60 ° C. for 4 hours. The solution was cooled in an ice bath to bring the internal temperature to 5 ° C. A solution in which 41.2 g of dicyclohexylcarbodiimide (0.2 mol) was dissolved in 50 g of GBL was added dropwise to this solution over 1 hour. Two more
7.6 g of 4-diamino-6-hydroxypyrimidine
(0.06 mol), a solution in which 8.0 g (0.04 mol) of 4,4′-diaminodiphenyl ether was dissolved in 150 g of GBL was added dropwise over 30 minutes. This solution was reacted for 3 hours under ice cooling. After the reaction, the precipitated urea compound was removed by filtration. The filtrate was poured into 5 l of water to produce a polyamic acid ester precipitate. This precipitate was collected, washed with water and methanol, and dried at 50 ° C. for 24 hours in a vacuum drier. 10 g of this polymer and 2 g of the naphthoquinonediazide compound having the chemical structure (14) were dissolved in 45 g of GBL to obtain a varnish D of a photosensitive composition. A varnish D of a photosensitive composition was applied on a 4-inch silicon wafer so that the film thickness after prebaking was 4 μm, and then a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) was used. Then, prebaking was performed at 100 ° C. for 3 minutes to obtain a photosensitive composition film. Next, the mask with the pattern cut was set in an exposure machine (Contact Aligner PLA-501F manufactured by Canon Inc.), and the exposure amount was set to 500 mJ / cm2 (405).
(intensity of nm). Development is Dainippon Screen
Using a SCW-636 developing device manufactured by Nippon Manufacturing Co., a 1.4% aqueous solution of tetramethylammonium was sprayed at 50 rpm for 10 seconds. After that, it is left still for 120 seconds,
Rinsing treatment was performed by spraying water for 0 second, and shake-drying was performed at 3000 rotations for 10 seconds. The film thickness of the unexposed portion after development was 3.5 μm, and the reduction in the thickness of the unexposed portion due to development was as very good as 0.5 μm. Furthermore, as a result of observing the pattern after development after development, a 10 μm pattern that can sufficiently withstand the demand as a buffer coat for semiconductors was resolved, and there was no problem with the pattern shape.

As a result of an organic solvent resistance test, there was no problem in solubility in fuming nitric acid. The imidation ratio of this varnish is 6
%Met. The water absorption was 9%.

Example 5 32.2 g (0.1 mol) of BTDA was dissolved in 200 g of GBL under a stream of dry nitrogen. 9.2 g of ethanol (0.2 mol) and 14 g of pyridine were added thereto and reacted at 50 ° C. for 3 hours. The solution was cooled in an ice bath to bring the internal temperature to 5 ° C. A solution in which 41.2 g of dicyclohexylcarbodiimide (0.2 mol) was dissolved in 50 g of GBL was added dropwise to this solution over 1 hour. Further, a solution in which 36.6 g (0.1 mol) of HAB was dissolved in 150 g of GBL was dropped over 30 minutes. This solution was reacted for 3 hours under ice cooling. After the reaction, the precipitated urea compound was removed by filtration. The filtrate was poured into 5 l of water to produce a polyamic acid ester precipitate. This precipitate was collected, washed with water and methanol, and dried at 50 ° C. for 24 hours in a vacuum drier. 10 g of this polymer and 2 g of a naphthoquinonediazide compound having the chemical structure (14) were dissolved in 40 g of GBL to obtain a varnish E of a photosensitive composition having a viscosity of 2.5 Pa · s at 25 degrees. A varnish E of a photosensitive composition is applied on a 6-inch silicon wafer so that the film thickness after prebaking is 5 μm, and then a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) is used. Then, by pre-baking at 100 ° C. for 3 minutes, a photosensitive heat-resistant resin precursor film was obtained. Next, an exposure machine (Nikon g-line stepper-NS)
R-1505-g6E), the reticle with the cut pattern was set, and g-line exposure was performed at an exposure amount of 500 mJ / cm 2 (intensity of 436 nm). For development, a 1.4% tetramethylammonium aqueous solution was sprayed for 10 seconds at 50 rotations using a developing device of SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd. Then, it was left still for 60 seconds, rinsed by spraying water at 400 rotations for 10 seconds, and shake-dried at 3000 rotations for 10 seconds. The film thickness of the unexposed portion after development was 3.7 μm, and the film loss of the unexposed portion due to development was 1.
It was as good as 3 μm. Furthermore, as a result of observing the pattern after development after development, a 5 μm pattern that can sufficiently withstand the demand as a semiconductor buffer coat was resolved,
There was no problem with the pattern shape.

The results of the test for resistance to organic solvents were satisfactory, but the fuming nitric acid treatment left a 200 Å film. This varnish has an imidation ratio of 15% and a water absorption of 11%.
Met.

Example 6 29.4 g (0.1 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was added in a dry nitrogen gas stream to GB.
L was dispersed in 400 g. 8.9 g of 1-butanol (0.12 mol), 1.4 g of water (0.08 mol) and 14 g of pyridine were added thereto and reacted at 60 ° C. for 6 hours. Here, 15.1 g (0.07 mol) of HAB and 3.2 g (0.03 mol) of paraphenylenediamine were added to GBL.
A solution dissolved in 150 g was added, the mixture was cooled in an ice bath, and the internal temperature was adjusted to 5 ° C. A solution in which 41.2 g of dicyclohexylcarbodiimide (0.2 mol) was dissolved in 50 g of GBL was added dropwise to this solution over 1 hour. This solution was reacted under ice cooling for 3 hours, and then at 20 ° C. for 1 hour. After the reaction, the precipitated urea compound was removed by filtration.
The filtrate was poured into 5 l of water to produce a polymer precipitate.
This precipitate was collected, washed with water and methanol, and dried at 50 ° C. for 24 hours in a vacuum drier. 10 g of this polymer
And 2 g of a naphthoquinonediazide compound having the chemical structure (12)
Was dissolved in 45 g of N-methyl-2-pyrrolidone to give 25 g
Varnish F of photosensitive composition having a viscosity of 1.8 Pa · s
Obtained. A varnish F of a photosensitive composition was applied on a 4-inch silicon wafer so that the film thickness after prebaking was 4 μm, and then a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) was used. Then, prebaking was performed at 100 ° C. for 3 minutes to obtain a photosensitive composition film. Next, an exposure machine (Canon contact aligner PLA-501) was used.
In F), a mask with a pattern cut was set, and exposure was performed at an exposure amount of 300 mJ / cm2 (intensity of 365 nm).
For development, a 1.4% tetramethylammonium aqueous solution was sprayed for 10 seconds at 50 rotations using a developing device of SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd. Then, it was left still for 120 seconds, rinsed by spraying water at 400 rotations for 10 seconds, and shake-dried at 3000 rotations for 10 seconds. The film thickness of the unexposed portion after development was 3.0 μm, and the reduction in the thickness of the unexposed portion due to development was very good at 1.0 μm. Further, as a result of observing the developed pattern after the development, an 8 μm pattern which can sufficiently withstand the demand as a semiconductor buffer coat was resolved, and the pattern shape was not a problem.

The results of the test for resistance to organic solvents were satisfactory, but a 1.0 μm film remained after the fuming nitric acid treatment. The varnish had an imidation ratio of 8% and a water absorption of 6%.

Comparative Example 1 In a 1-liter four-necked flask, 10.1 g (0.95 mol) of 4,4-diaminodiphenyl ether, S
1.24 g (0.005 mol) of iDA is 200 g of NMP
And BTDA (16.1 g, 0.05 mol) and PMDA (10.7 g, 0.048 mol) were added thereto and reacted at room temperature for 1 hour and then at 50 ° C. for 3 hours to obtain a polyamic acid. Example 1 was added to this polyamic acid solution.
The photosensitive components were added at the same ratio as in Example 1 and the viscosity at 25 degrees was 3.
Varnish G of a photosensitive composition having a pressure of 0 Pa · s was obtained. A varnish G of a photosensitive composition was applied on a 6-inch silicon wafer so that the film thickness after prebaking was 4 μm, and then a hot plate (SCW-63 manufactured by Dainippon Screen Mfg. Co., Ltd.) was used.
Using 6), prebaking was performed at 100 ° C. for 3 minutes to obtain a photosensitive composition film. Next, the reticle with the pattern cut was set in an exposure machine (Nikon g-line stepper-NSR-1505-g6E), and the exposure amount was 500 mJ / c.
g-line exposure was performed at m2 (intensity of 436 nm). For the development, a 0.5% aqueous solution of tetramethylammonium was sprayed at 50 rpm for 10 seconds using a developing device of SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd. Thereafter, the mixture was allowed to stand still for 60 seconds, then sprayed with a developer at 400 rotations for 5 seconds, sprayed with water at 400 rotations for 10 seconds, rinsed, and shake-dried at 3000 rotations for 10 seconds to dry. The pattern after development did not become a positive image in which the exposed portion dissolved but became a negative image. Further, it was found that the film thickness after development was extremely thin, 1.5 μm, and the decrease in the film was 2.5 μm, which was low in contrast.

As a result of an organic solvent resistance test, there was no problem in solubility in fuming nitric acid. The imidation ratio of this varnish is 1
The water absorption was 5% and the water absorption was 2.5%.

Comparative Example 2 Under dry nitrogen flow, 10.9 g (0.05 mol) of PMDA and 16.1 g (0.05 mol) of BTDA were added to GBL2.
Was dissolved in 00 g. 9.2 g of ethanol (0.2 mol) and 14 g of pyridine were added thereto and reacted at 50 ° C. for 3 hours. The solution was cooled in an ice bath to bring the internal temperature to 5 ° C. A solution in which 41.2 g of dicyclohexylcarbodiimide (0.2 mol) was dissolved in 50 g of GBL was added dropwise to this solution over 1 hour. Further BA
10.9 g (0.03 mol) of HF and 14.0 g (0.07 mol) of 4,4′-diaminodiphenyl ether were added to GB.
A solution dissolved in 150 g of L was dropped over 30 minutes.
This solution was reacted for 3 hours under ice cooling. After the reaction, the precipitated urea compound was removed by filtration. The filtrate was poured into 5 l of water to produce a polyamic acid ester precipitate. The precipitate is collected, washed with water and methanol, and dried in a vacuum drier.
Dried at 0 degrees for 24 hours. 10 g of this polymer and 2 g of a naphthoquinonediazide compound of chemical structure (12) were
It was dissolved in 30 g to obtain a varnish H of a photosensitive composition having a viscosity at 25 degrees of 2.0 Pa · s. A varnish H of a photosensitive composition was applied on a 4-inch silicon wafer so that the film thickness after prebaking was 5 μm, and then a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) was used. Then, prebaking was performed at 100 ° C. for 3 minutes to obtain a photosensitive composition film. Next, the mask with the pattern cut was set in an exposure machine (Contact Aligner PLA-501F manufactured by Canon Inc.), and the exposure amount was set to 500 mJ / cm2 (405).
(intensity of nm). Development is Dainippon Screen
Using a SCW-636 developing device manufactured by Nippon Manufacturing Co., a 1.4% aqueous solution of tetramethylammonium was sprayed at 50 rpm for 10 seconds. After that, it is left still for 600 seconds,
Rinsing treatment was carried out by spraying water for 0 second, and shake-drying was performed at 3000 rpm for 10 seconds, but all were dissolved, and a pattern could not be obtained.

As a result of the test for resistance to organic solvents, there was no problem in solubility in fuming nitric acid. The imidation ratio of this varnish is 5
% And the water absorption were 5%.

Comparative Example 3 10.9 g (0.05 mol) of PMDA and 16.1 g (0.05 mol) of BTDA were mixed with GBL2 in a stream of dry nitrogen.
Was dissolved in 00 g. To this, 54 g of stearyl alcohol (0.2 mol) and 14 g of pyridine were added and reacted at 60 ° C. for 8 hours. The solution was cooled in an ice bath to bring the internal temperature to 5 ° C. A solution in which 41.2 g of dicyclohexylcarbodiimide (0.2 mol) was dissolved in 50 g of GBL was added dropwise to this solution over 1 hour. Further, a solution in which 36.6 g (0.1 mol) of BAHF was dissolved in 150 g of GBL was added dropwise over 30 minutes. This solution was reacted for 3 hours under ice cooling. After the reaction, the precipitated urea compound was removed by filtration. The filtrate was poured into 5 l of water to produce a polyamic acid ester precipitate. This precipitate was collected, washed with water and methanol, and dried at 50 ° C. for 24 hours in a vacuum drier. 10 g of this polymer and 2 g of the naphthoquinonediazide compound having the chemical structure (11) were dissolved in 25 g of GBL to obtain a varnish I of a photosensitive composition having a viscosity of 1.5 Pa · s at 25 degrees. Varnish I of the photosensitive composition was applied on a 4-inch silicon wafer so that the film thickness after prebaking was 5 μm, and then a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) was used. And 3 at 100 ° C
By pre-baking, a photosensitive composition film was obtained.
Next, an exposure machine (Canon contact aligner P)
LA-501F), the mask with the pattern cut was set, and exposure was performed at an exposure amount of 500 mJ / cm2 (intensity of 405 nm). Developed 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. After that, it was left standing for 600 seconds, rinsed by spraying water at 400 rotations for 10 seconds, and shake-dried at 3000 rotations for 10 seconds, but neither the exposed part nor the unexposed part was dissolved, and a pattern could be obtained. I could not do it.

As a result of an organic solvent resistance test, there was no problem in solubility in fuming nitric acid. The imidation ratio of this varnish is 1
0% and water absorption were 4%.

Example 7 16.6 g (0.05 mol) of BTDA under a stream of dry nitrogen
Was dissolved in 100 g of GBL. To this, 4.6 g of ethanol (0.1 mol) and 7 g of pyridine were added and reacted at 50 ° C. for 3 hours. The solution was cooled in an ice bath to bring the internal temperature to 5 ° C. Here, a solution in which 41.2 g of dicyclohexylcarbodiimide (0.2 mol) was dissolved in 100 g of GBL was dropped into this solution over 1 hour. Further, a solution in which 10.8 g (0.05 mol) of HAB and 10.0 g (0.05 mol) of 4,4′-diaminodiphenyl ether were dissolved in 150 g of GBL was added dropwise over 30 minutes. The mixture was further reacted in an ice bath for 2 hours, the solution temperature was adjusted to 20 ° C, and 14.7 g (0.05 mol) of BPDA was added to GBL.
Added with 30 ml. Then, at 20 degrees for 1 hour, 5
The reaction was performed at 0 degrees for 2 hours. After the reaction, the precipitated urea compound was removed by filtration. The filtrate was poured into 5 l of water to produce a polymer precipitate. This precipitate was collected, washed with water and methanol, and dried at 50 ° C. for 24 hours in a vacuum drier. 10 g of this polymer and 3 g of the naphthoquinonediazide compound having the chemical structure (14) were dissolved in 50 g of GBL to give 2 g
A varnish J of a photosensitive composition having a viscosity at 5 degrees of 2.0 Pa · s was obtained. A varnish J of a photosensitive composition was applied on a 4-inch silicon wafer so that the film thickness after prebaking was 5 μm, and then a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) was used. Then, prebaking was performed at 100 ° C. for 3 minutes to obtain a photosensitive composition film. Then
Exposure machine (Canon contact aligner PLA-5)
01F), the mask with the pattern cut was set, and exposure was performed at an exposure amount of 500 mJ / cm2 (intensity of 405 nm). Development was carried out by SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.
Was sprayed with a 1.4% aqueous solution of tetramethylammonium for 10 seconds at 50 rotations. After this, 120
After standing still for 400 seconds, water was sprayed at 400 rotations for 10 seconds to perform a rinsing treatment, and the mixture was shaken off at 3000 rotations for 10 seconds and dried. The film thickness of the unexposed portion after development was 3.8 μm, and the reduction of the film in the unexposed portion due to development was very good at 1.2 μm. Furthermore, as a result of observing the pattern after development after development, a 10 μm pattern that can sufficiently withstand the demand as a buffer coat for semiconductors was resolved, and there was no problem with the pattern shape.

As a result of an organic solvent resistance test, there was no problem in solubility in fuming nitric acid. The imidation ratio of this varnish is 1
5%. The water absorption was 8%.

COMPARATIVE EXAMPLE 4 36.6 g (0.1 mol) of BAHF and 11.1 g (0.11 mol) of triethylamine were dissolved in 200 ml of NMP. The solution was cooled to −10 ° C., and 20.3 g (0.1 mol) of isophthalic dichloride was added to GBL100 m
The resulting solution was added dropwise over 1 hour so that the temperature of the reaction solution did not exceed 0 ° C. After completion of the dropwise addition, the reaction solution was reacted at −10 ° C. for 30 minutes and then at 10 ° C. for 5 hours.
After completion of the reaction, the solution was poured into 10 l of water to obtain a polymer precipitate. The precipitate was collected by filtration and dried in vacuo at 50 ° C. for 24 hours. After vacuum drying, 12 g of this polymer, 3 g of a naphthoquinonediazide compound having the chemical structure (12) and G
Dissolved in BL30g, viscosity at 25 degrees is 1.5Pa.
varnish (K) of the photosensitive composition of Example s was obtained. A varnish K of a photosensitive composition was applied on a 6-inch silicon wafer so that the film thickness after prebaking was 5 μm, and then a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) was used. Then, prebaking was performed at 100 ° C. for 3 minutes to obtain a photosensitive composition film. Then, the reticle with the pattern cut was set in an exposure machine (i-line stepper NSR-1755-i7A manufactured by Nikon Corporation), and the exposure amount was 200 mJ / cm @ 2.
(Intensity of 365 nm). For development, a 1.5% aqueous solution of tetramethylammonium was sprayed at 50 rpm for 10 seconds using a developing device of SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd. Then, it was left still at 0 rotation for 70 seconds, rinsed with water at 400 rotations, and shake-dried at 3000 rotations for 10 seconds. The film thickness of the unexposed portion after the development was 4.8 μm, and the reduction of the film in the unexposed portion due to the development was as very good as 0.2 μm. Further, as a result of observing the developed pattern after the development, a 5 μm pattern which can sufficiently withstand the requirements as a buffer coat for semiconductors was resolved, and the pattern shape was not a problem.

Cracks were observed in the organic solvent resistance test, and a film as large as 6 μm remained in the fuming nitric acid treatment, indicating that there was a problem. Since this varnish is not a polyimide precursor, there is no imidization rate. The water absorption was 1%.

Example 8 10 g of the polymer synthesized in Example 1, 3 g of the polymer synthesized in Comparative Example 4, and 3 g of the naphthoquinonediazide compound having the chemical structure (12) were dissolved in 30 g of GBL, and the viscosity at 25 degrees was 2.0 Pa · varnish (L) of the photosensitive composition of Example s was obtained.

A varnish L of the photosensitive composition was applied on a 6-inch silicon wafer so that the film thickness after prebaking was 5 μm, and then a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) was used. Was prebaked at 100 ° C. for 3 minutes to obtain a photosensitive composition film. Next, an exposure machine (Nikon i-line stepper-NSR-175)
5-i7A), the reticle with the pattern cut was set, and i-line exposure was performed at an exposure amount of 200 mJ / cm2 (intensity of 365 nm). Developed by SC manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a developing device of W-636, a 1.5% aqueous solution of tetramethylammonium was sprayed at 50 rpm for 10 seconds. Then, it was left still at 0 rotation for 70 seconds, rinsed with water at 400 rotations, and shake-dried at 3000 rotations for 10 seconds. The film thickness of the unexposed portion after development was 4.5 μm,
The film loss of the unexposed portion due to the development was as very good as 0.5 μm. Further, as a result of observing the developed pattern after the development, a 5 μm pattern which can sufficiently withstand the requirements as a buffer coat for semiconductors was resolved, and the pattern shape was not a problem.

As a result of an organic solvent resistance test, there was no problem in solubility in fuming nitric acid. The imidation ratio of this varnish is 1
0% and water absorption were 4%.

Example 9 18.0 g of the diamine compound (1) synthesized in Synthesis Example 1
(47.5 mmol) and 0.62 g (2.5 mmol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were dissolved in 80 g of NMP at room temperature. Here B
14.4 g (49 mmol) of PDA were added along with 20 g of NMP. The solution is allowed to stand at room temperature for 1 hour,
Allowed to react for hours. To 30 g of this solution was added 1.5 g of a naphthoquinonediazide compound having the chemical structure (11) together with 8 g of GBL to obtain a photosensitive composition (M) having a viscosity of 1 Pa · s.

On a 4-inch silicon wafer, a varnish M of a photosensitive composition was applied so that the film thickness after prebaking was 5 μm, and then a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) was applied. Was prebaked at 100 ° C. for 3 minutes to obtain a photosensitive composition film. Then, an exposure machine (Canon contact aligner PLA)
At -501F), the mask with the pattern cut was set, and exposure was performed at an exposure amount of 200 mJ / cm2 (intensity of 365 nm). Developed by SCW- manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a 636 developing device, a 1.5% aqueous solution of tetramethylammonium was sprayed at 50 rpm for 10 seconds. Then, it was left still at 0 rotation for 40 seconds, rinsed with water at 400 rotations, and shake-dried at 3000 rotations for 10 seconds. The film thickness of the unexposed portion after development was 4.0 μm, and the film thickness of the unexposed portion after development was as good as 1.0 μm. Furthermore, as a result of observing the pattern after development after development, a 10 μm pattern that can sufficiently withstand the demand as a buffer coat for semiconductors was resolved, and there was no problem with the pattern shape.

As a result of the test for organic solvent resistance, there was no problem in solubility in fuming nitric acid. The imidation ratio of this varnish is 1
The water absorption was 5% and the water absorption was 2%.

Example 10 22.3 g of the diamine compound (16) synthesized in Synthesis Example 2
(47.5 mmol) and 0.62 g (2.5 mmol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were dissolved in 120 g of NMP at room temperature. To this was added 14.4 g (49 mmol) of BPDA along with 20 g of NMP. This solution was reacted at room temperature for 1 hour and then at 50 ° C. for 3 hours. The chemical structure (13) is added to 30 g of this solution.
Was added together with 2 g of GBL to obtain a photosensitive composition (N) having a viscosity of 1.2 Pa · s. A varnish N of a photosensitive composition was applied on a 4-inch silicon wafer so that the film thickness after prebaking was 5 μm, and then a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) was used. Then, prebaking was performed at 100 ° C. for 3 minutes to obtain a photosensitive composition film. Then, an exposure machine (Canon contact aligner PLA)
At -501F), the mask with the pattern cut was set, and exposure was performed at an exposure amount of 200 mJ / cm2 (intensity of 365 nm). Developed by SCW- manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a 636 developing device, a 1.5% aqueous solution of tetramethylammonium was sprayed at 50 rpm for 10 seconds. Then, it was left still at 0 rotation for 30 seconds, rinsed with water at 400 rotations, and shake-dried at 3000 rotations for 10 seconds. The film thickness of the unexposed portion after the development was 4.2 μm, and the reduction in the film thickness of the unexposed portion due to the development was as very good as 0.8 μm. Furthermore, as a result of observing the pattern after development after development, a 10 μm pattern that can sufficiently withstand the demand as a buffer coat for semiconductors was resolved, and there was no problem with the pattern shape.

As a result of an organic solvent resistance test, there was no problem in solubility in fuming nitric acid. The imidation ratio of this varnish is 1
The water absorption was 5% and the water absorption was 2.5%.

Example 11 Under dry nitrogen, 16.1 g (50 mmol) of BTDA, 4.6 g (100 mmol) of ethanol, and 7.9 of pyridine
g (100 mmol) was dissolved in 200 g of GBL and 5 g
The reaction was performed at 0 ° C. for 2 hours. Here, 18.1 g (30 mmol) of the diamine compound (17) synthesized in Synthesis Example 3 and B
11.0 g (30 mmol) of AHF and 4-DAE 8.0
g (40 mmol) was added to a solution of 150 g of GBL, and the temperature of the solution was adjusted to 5 ° C. Further, a solution in which 20.6 g (100 mmol) of dicyclohexylcarbodiimide was dissolved in 30 g of GBL was added dropwise. After completion of the dropwise addition, the temperature of the solution was raised to room temperature, and 10.9 g (50 mmol) of PMDA was added to NM.
Added with P10g. This solution was reacted at room temperature for 1 hour and then at 50 ° C. for 3 hours. After completion of the reaction, the precipitate was removed by filtration, and the filtrate was poured into 10 l of water to obtain a polymer precipitate. The polymer was collected by filtration and dried at 50 ° C. in vacuo. After vacuum drying, 10g of polymer and chemical structure (11)
2.2 g of naphthoquinonediazide compound of GBL 30 g
In addition, a photosensitive composition (O) having a viscosity of 2.5 Pa · s was obtained. A varnish O of a photosensitive composition was applied on a 4-inch silicon wafer so that the film thickness after prebaking was 5 μm, and then a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) was used. Then, the photosensitive composition was obtained by pre-baking at 100 ° C. for 3 minutes. Then, an exposure machine (Canon contact aligner PLA)
At -501F), the mask with the pattern cut was set, and exposure was performed at an exposure amount of 300 mJ / cm2 (intensity of 365 nm). Developed by SCW- manufactured by Dainippon Screen Mfg. Co., Ltd.
Using a 636 developing device, a 1.5% aqueous solution of tetramethylammonium was sprayed at 50 rpm for 10 seconds. Thereafter, the plate was left standing at 0 rotation for 60 seconds, rinsed with water at 400 rotations, and shake-dried at 3000 rotations for 10 seconds. The film thickness of the unexposed portion after the development was 4.2 μm, and the reduction in the film thickness of the unexposed portion due to the development was as very good as 0.8 μm. Furthermore, as a result of observing the pattern after development after development, a 10 μm pattern that can sufficiently withstand the demand as a buffer coat for semiconductors was resolved, and there was no problem with the pattern shape.

As a result of an organic solvent resistance test, there was no problem in solubility in fuming nitric acid. The imidation ratio of this varnish is 5
% And the water absorption were 5%.

Example 12 The diamine compound (1) synthesized in Synthesis Example 4 under dry nitrogen
8) 12.2 g (0.05 mol) was dissolved in 100 g of NMP. Here, 16.1 g (0.05 mol) of BTDA
Was added with 13 g of NMP, and the mixture was added at room temperature for 1 hour,
The reaction was performed at 0 ° C. for 3 hours. 40 g of this solution and 1.8 g of the naphthoquinonediazide compound (2) were added together with 2 g of GBL to obtain a photosensitive composition (P) having a viscosity of 1.5 Pa · s. A varnish P of a photosensitive composition is applied on a 4-inch silicon wafer so that the film thickness after prebaking is 5 μm, and then a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) is used. Then, the photosensitive composition was obtained by pre-baking at 100 ° C. for 3 minutes. Next, an exposure machine (Canon contact aligner PLA-501) was used.
In F), a mask with a cut pattern was set, and exposure was performed at an exposure amount of 300 mJ / cm2 (intensity of 365 nm).
For development, a 1.2% aqueous solution of tetramethylammonium was sprayed at 50 rpm for 10 seconds using a developing device of SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd. After that, it is left still for 45 seconds at 0 rotation, rinsed with water at 400 rotations,
The mixture was shaken off at 00 rotation for 10 seconds and dried. The film thickness of the unexposed portion after development was 3.8 μm, and the reduction of the film in the unexposed portion due to development was very good at 1.2 μm. Furthermore, as a result of observing the pattern after development after development, 10 μm which can sufficiently withstand the demand as a buffer coat for semiconductors was obtained.
Was resolved, and there was no problem with the pattern shape.

As a result of an organic solvent resistance test, there was no problem in solubility in fuming nitric acid. The imidation ratio of this varnish is 1
The water absorption was 5% and the water absorption was 2%.

Example 13 12.1 g (0.02 mol) of diamine (19) was added to NMP
Dissolved in 32 g. Here, 6.2 g of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride
(0.02 mol) was added along with 11 g of NMP. 30
After stirring at 4 ° C. for 4 hours, 40 g of acetone was added, and 1.6 g (0.016 mol) of acetic anhydride and 1.3 g of pyridine were further added to partially imidize 45% of the polyimide precursor. After stirring at 30 ° C. for 1 hour, this solution was poured into 2000 ml of water to obtain a polyimide precursor precipitate. The precipitate was collected by filtration and dried in vacuum at 80 ° C. for 20 hours. 9 g of this precipitate was treated with gamma-butyrolactone 21
g, and 4NT-300 (manufactured by Toyo Gosei Co., Ltd., 2,3,3) as a naphthoquindiazidesulfonic acid ester.
1.8 g of 4,4′-tetrahydroxybenzophenone (an average of three naphthoquindiazide sulfonic acid esters) was added to obtain a positive photosensitive polyimide precursor solution.

This solution was spin-coated on a 4-inch silicon wafer using SCW-636 manufactured by Dainippon Screen Co., Ltd. so that the film thickness after baking at 120 ° C. for 3 minutes was 5 μm. After application, SCW-63 manufactured by Dainippon Screen Co., Ltd.
6 was prebaked on a hot plate at 120 ° C. for 3 minutes. After pre-baking, using a contact aligner PLA-501 manufactured by Canon Inc., 300 mJ / c
Exposure was performed using a test pattern of m2 (measured value at 365 nm) as a mask. After the exposure, the film was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide for 40 seconds, and then rinsed with pure water for 10 seconds to perform development. The film thickness of the unexposed portion after the development was 4.2 μm, and the reduction of the film by the development was as small as 0.8 μm, which was good.

As a result of visual inspection of the developed pattern with an optical microscope, a 2-micron line was resolved, and there was no problem with the pattern shape.

As a result of an organic solvent resistance test, there was no problem in solubility in fuming nitric acid. The imidation ratio of this varnish is 4
The water absorption was 7% and the water absorption was 2%.

[0097]

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.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/11 501 G03F 7/11 501 H01L 21/027 H01L 21/30 502R

Claims (6)

[Claims] (A) General formula (1) (Wherein, R ₁ is a trivalent or tetravalent organic group having at least 2 carbon atoms, R ₂ is a tri- to hexavalent organic group having at least 2 carbon atoms, R ₃ is a hydrogen atom or A monovalent organic group having 1 to 10 carbon atoms, and n
Is an integer from 10 to 100000, m is 1 or 2,
p is an integer from 1 to 4. (B) a quinonediazide compound; and (b) a quinonediazide compound. 2. A polymer represented by the general formula (2) with respect to 100 parts by weight of the polymer represented by the general formula (1). (Wherein, R ₄ is a divalent organic group containing at least 2 carbon atoms, R ₅ is a trivalent to hexavalent group having at least 2 carbon atoms, m is an integer from 10 to 10,000,
q is an integer of 1 to 6. 1)
0 to 200 parts by weight, 5 to 10 parts of the quinonediazide compound
2. The photosensitive composition according to claim 1, which contains 0 parts by weight. 3. A polymer represented by the general formula (3) with respect to 100 parts by weight of the polymer represented by the general formula (1). (Wherein, R ₆ is a tri- to tetra-valent organic group containing at least 2 carbon atoms, R ₇ is a di-valent group having at least 2 carbon atoms, R ₈ is hydrogen or C 1 to C 20 The organic group, r is an integer of from 10 to 10000, and s is an integer of from 1 to 2.) 1 to 50 parts by weight of a polymer represented by the formula (1) and 5 to 100 parts by weight of a quinonediazide compound. Composition. 4. A compound represented by the formula (1) wherein R ₂ is represented by the formula (4): (Wherein, R ₉ has 3 to 20 carbon atoms having a hydroxyl group of 3 to 20)
A hexavalent organic group, R ₁₀ is an organic group having 2 to 10 carbon atoms, R ₁₁
Is a trivalent to hexavalent organic group having a hydroxyl group having 3 to 20 carbon atoms, and t and u are each an integer of 1 to 4. The photosensitive composition according to claim 1, which is represented by the formula: 5. A compound of the formula (1) wherein R ₂ is a compound of the formula (5) (Wherein, R ₁₂ is a divalent organic group having a hydroxyl group having 3 to 20 carbon atoms, and R ₁₃ is a divalent organic group having a hydroxyl group having 3 to 20 carbon atoms.)
To a hexavalent organic group, and v is an integer of 1 to 4. The photosensitive composition according to claim 1, which is represented by the formula: 6. A compound represented by the general formula (1) wherein R ₂ is represented by the general formula (6): (Wherein, R ₁₄ and R ₁₆ are both divalent organic groups having a hydroxyl group having 3 to 20 carbon atoms, R ₁₅ is a trivalent to hexavalent organic group having a hydroxyl group having 3 to 20 carbon atoms, w is The photosensitive composition according to claim 1, which is an integer of 1 to 4.