JPH11181089A - Photosensitive and heat-resistant resin precursor composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition developable in a wide range of alkali concentration, highly sensitive, therefore, capable of reducing film loss of unexposed portions while developing and useful for e.g. protective films for semiconductor elements, by using a polymer having a specific protective hydroxydiamino structure in its molecule. SOLUTION: This photosensitive and heat-resistant resin precursor composition comprises (A) a polymer of the formula [R1 is a divalent 2-30C organic group, for example, a phthalic acid residue or a biphenyl ether dicarboxylic acid residue; R2 is a trivalent to hexavalent 6-40C organic group, for example, 2,2-bis(m-amino-p-hydroxy-phenyl)hexafluoropropane residue; R3 contains 10-50 mol.%, based on the total, of naphthoquinone diazidosulfonyl group and the balance being H; (p) is 1-4; (n) is 10-100,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive heat-resistant resin precursor composition useful as a surface protective film for semiconductors, and more particularly to a positive photosensitive photosensitive composition which can be developed with a developer having a wide alkali concentration range and has high sensitivity. The present invention relates to a resin precursor composition.

[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 naphthoquinonediazide added to a polyamic acid (JP-A-52-1)
No. 3315), a product obtained by adding naphthoquinonediazide to a soluble polyimide having a hydroxyl group (JP-A-64-6).
No. 0630), a polyamide obtained by adding a naphthoquinonediazide to a polyamide having a hydroxyl group (JP-A-56-2714).
No. 0) is known.

[0003]

However, when a naphthoquinonediazide is added to a polyamic acid, the solubility of the carboxyl group of the polyamic acid is high due to the dissolution inhibiting effect of naphthoquinonediazide on alkali.
In most cases, a desired pattern cannot be obtained. 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. Also in the case of adding a naphthoquinonediazide to a polyamide resin having a hydroxyl group, there has been a problem that there is a limitation in the structure in order to obtain solubility.

Further, the structure of a soluble polyimide having a phenolic hydroxyl group in which a naphthoquinonediazidosulfonyl group is introduced into the phenolic hydroxyl group through an ester bond (Japanese Patent Application Laid-Open No. 3-58048) is limited in order to make it soluble. In addition, there is a disadvantage that the obtained film has poor organic solvent resistance.

Further, as a developer used in these products, an aqueous solution of a weakly alkaline tertiary amine or an aqueous solution of an inorganic alkali salt such as sodium phosphate has been used.

In order to increase the sensitivity, the esterification rate of the naphthoquinonediazidesulfonic acid ester compound is generally lowered or the amount of the naphthoquinonediazidesulfonic acid ester compound is reduced. There were problems such as a significant decrease in thickness.

A photoresist developing solution generally used in semiconductor manufacturing is a 2.38% aqueous solution of tetramethylammonium hydroxide. For this reason, it is desirable that photosensitive polyimide can be developed with this 2.38% aqueous solution of tetramethylammonium hydroxide. Further, it is preferable that a different developing solution can be used without any problem even if a different developing solution is used in the future.

Further, from the viewpoint of reducing the manufacturing cost, it is desirable that the sensitivity is high and the film loss of the unexposed portion during development is small.

In view of the above, it is an object of the present invention to provide a positive photosensitive heat-resistant resin precursor composition which can be developed in a wide range of alkali concentrations, has high sensitivity, and has little film loss in unexposed areas during development. It is assumed that.

[0010]

According to the present invention, there is provided a compound represented by the general formula (1):
Is a photosensitive heat-resistant resin precursor composition characterized by a polymer represented by the formula:

[0011]

Embedded image (Wherein, R1 is a divalent organic group having 2 to 30 carbon atoms,
R2 is a trivalent to hexavalent organic group having 6 to 40 carbon atoms,
R3 contains at least 10 to 50 mol% of a naphthoquinonediazidosulfonyl group, the rest being hydrogen atoms, n is an integer from 10 to 100,000, and p is an integer from 1 to 4. )

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer represented by the general formula (1) in the present invention can be a polymer which forms an oxazole ring by heating or an appropriate catalyst.

In the general formula (1), R1 represents a structural component of a dicarboxylic acid, and the dicarboxylic acid is preferably a divalent group containing an aromatic ring and having 2 to 30 carbon atoms. Specifically, phthalic acid residue, diphenyl ether dicarboxylic acid residue, naphthalenedicarboxylic acid residue, dicarboxydiphenylhexafluoropropane residue, dicarboxydiphenylpropane residue, benzophenonedicarboxylic acid residue, diphenylsulfonedicarboxylic acid residue And the like, but are not limited thereto. In addition, as long as there is no problem with the heat resistance and solvent resistance of the obtained heat-resistant resin,
Aliphatic dicarboxylic acids such as adipic acid residue, oxalic acid residue and cyclohexanedicarboxylic acid residue can also be copolymerized. The copolymerization amount of such an aliphatic dicarboxylic acid is preferably 1 to 30 mol% of the acid component. If the content is 30 mol% or more, the heat resistance of the obtained film decreases, which is not preferable.

In the above formula (1), R2 represents a structural component of a protected hydroxydiamino compound. Among them, a preferable example of R2 is 2,2-bis (m-
(Amino-p-hydroxyphenyl) hexafluoropropane residue, 3,3′-dihydroxy-4,4′-diaminobiphenyl residue, 3,3′-dihydroxy-4,4 ′
-Diaminodiphenyl ether residue, 4,4'-dihydroxy-3,3'-diaminodiphenylsulfone residue,
Hydroxy-metaphenylenediamine residue, 2,2-bis (p-amino-m-hydroxyphenyl) hexafluoropropane residue, 3,3′-diamino-4,4′-dihydroxybiphenyl residue, 3-hydroxy- 1,5-
Diaminobenzene residue, 6-hydroxy-2,4-diaminopyrimidine residue, 5,6-diamino-2,4-dihydroxypyrimidine residue, 2,4-diamino-6-hydroxytriazine residue, diaminotrihydroxybenzene Preferred are a residue, a diaminotetrahydroxybenzene residue, a diaminotrihydroxynaphthalene residue, a diaminotetrahydroxynaphthalene residue, and a hydroxydiamine residue represented by the following formula (7).

[0015]

Embedded image Further, in the range of 1 to 30 mol% of the diamine component, a phenylenediamine residue having no hydroxyl group, a bis (trifluoromethyl) benzidine residue, a dimethylbenzidine residue, a diaminodiphenylether residue, a diaminodiphenylsulfone residue, (Aminophenoxy) benzene residue,
Bis (aminophenoxyphenyl) hexafluoropropane residue, bis (aminophenoxyphenyl) sulfone residue, bis (aminophenoxyphenyl) propane residue or other aromatic diamine residue, or ethylenediamine residue, hexamethylenediamine residue, Aliphatic diamine residues such as cyclohexyldiamine residue and methylenebiscyclohexylamine residue can also be copolymerized. If the copolymerization amount exceeds 30 mol%, there are problems that the heat resistance of the obtained heat-resistant resin is reduced, and that the solubility in an alkali developing solution is reduced in a developing treatment after light irradiation.

Further, a silicon atom-containing diamine residue can be used as R2 in order to improve the adhesion to a substrate. Such include 1,3-bis (3-
Aminopropyl) tetramethyldisiloxane residue, α,
ω-bis (4-aminophenyl) permethylpolysiloxane residue and the like. The copolymerization amount of such a silicon atom-containing diamine is 1
To 40 mol% is preferred.

R3 in the general formula (1) is preferably a group which becomes soluble in an aqueous alkali solution when irradiated with ultraviolet rays. Examples of such a compound include an orthonaphthoquinonediazidosulfonyl group, a hydroxyimide group and an oxime group, and an orthonaphthoquinonediazidosulfonyl group is preferred. This orthonaphthoquinonediazide group is decomposed by ultraviolet light to become indenecarboxylic acid,
Since the indene carboxylic acid is dissolved in the aqueous alkali solution, the solubility of the exposed portion and the unexposed portion in the aqueous alkali solution is greatly changed. In R3, the content of the orthonaphthoquinonediazidosulfonyl group is preferably 10 to 50 mol%. When the content is less than 10 mol%, the unexposed portion is easily dissolved in the aqueous alkali solution, so that a good pattern cannot be obtained. When the content is more than 50 mol%, the concentration of the orthonaphthoquinonediazidosulfonyl group becomes too high. In addition, since the orthonaphthoquinonediazidosulfonyl group is not completely decomposed during exposure in a practical range, the solubility of the exposed portion in an aqueous alkaline solution is reduced, and a pattern cannot be obtained. Thus, the more preferable orthonaphthoquinonediazidosulfonyl group of R3 is 15 to 40 mol%, and the rest is preferably a hydrogen atom. In addition to the hydrogen atom, an alkyl group such as a methyl group or an ethyl group can be modified by 10 to 20 mol% of R3 in order to adjust solubility in an alkaline aqueous solution.

In the present invention, the polymer represented by the general formula (2) can be a polymer that forms an imide ring by heating or an appropriate catalyst.

In the general formula (2), R4 represents a carboxylic acid component, and is preferably trivalent trimellitic acid, trimesic acid, tetravalent pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid. Trivalent or tetravalent groups having an aromatic group such as diphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, and (hexafluoroisopropylidene) diphthalic acid, but other aliphatic butanetetracarboxylic acids Compounds such as an acid, cyclopentanetetracarboxylic acid, and ethylenediaminetetraacetic acid can be copolymerized at 1 to 30 mol% of the acid component. If the copolymerization amount of these aliphatic acids exceeds 30 mol%, the heat resistance of the resulting film is undesirably reduced.

In the general formula (2), R5 represents a protected hydroxy group-containing diamino compound component;
Those having the same structure as the two components can be used as preferred compounds.

In the general formula (2), R6 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and its structure can be changed in view of the solubility of the obtained polymer. In other words, the solubility of hydrogen atoms in an aqueous alkali solution is very fast, and the dissolution rate decreases as the number of carbon atoms increases. On the other hand, when the number of carbon atoms exceeds 20, it does not dissolve in an alkaline aqueous solution. From these points, R6
May be used alone or a plurality of them may coexist to adjust the dissolution rate.

In the general formulas (2) and (3), R7, R
8 can be the same as R3 in formula (1).

In the general formula (3), R9 represents a carboxylic acid component having a protected hydroxyl group, and those having a structure as shown in the chemical formula (6) can be mentioned as preferred.

[0024]

Embedded image In the formula, R19 and R21 are a trivalent or tetravalent organic group having 2 to 30 carbon atoms, R20 is a trivalent to hexavalent organic group having 2 to 30 carbon atoms, R22 and R24 are a hydrogen atom, and / or
Or a monovalent organic group having 1 to 20 carbon atoms, R23 contains at least 10 to 50 mol% of a total of naphthoquinonediazidosulfonyl groups, the rest being hydrogen atoms, w and y are 1 to
Or 2, x represents an integer of 1 to 4. The structure of a specific compound of such a compound is shown in the following formula.

[0025]

Embedded image In the general formula (3), R10 represents a diamine component, such as phenylenediamine, diaminodiphenylether, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxy) benzene, and bis (aminophenoxyphenyl) sulfone. Aliphatic amines such as aromatic diamine, ethylenediamine, hexamethylenediamine, cyclohexyldiamine, methylenebiscyclohexylamine can be used.

In the general formula (4), R12 represents a carboxylic acid component, and the same as R4 in the general formula (2) can be used.

In the general formula (4), R13 represents a divalent group having 4 to 30 carbon atoms containing a silicon atom in an amount of 5 to 30 mol% of its constituent components, Shows up to 30 divalent organic groups. Examples of such a silicon atom-containing diamine compound include 1,3
-Bis (3-aminopropyl) tetramethyldisiloxane, α, ω-bis (γ-aminopropyl) hexamethyltetrasiloxane, 1,3-bis (4′-aminophenyl) tetramethyldisiloxane, terminal amino group modification Siloxane oil or the like can be used. As the diamine other than the silicon atom-containing diamine component, the same diamine as R10 in the general formula (3) can be used.

In the formula (4), the same R14 as R6 in the formula (2) can be used.

In the general formula (5), R15 represents a diimide residue, and R15 in the general formula (4) such as pyromellitic diimide, benzophenonetetracarboxylic diimide, biphenyltetracarboxylic diimide, diphenylethertetraruboxylic diimide, etc.
12 represents an imide-ring-closed component.

In the general formula (5), R16 represents an amino component, and the same as R12 in the general formula (4) can be used.

In the present invention, 10 to 40% of the polymers represented by the general formulas (2) and (3) can be imide-closed. Similarly, 20 to 50% of the polymer represented by the general formulas (2) and (3) may be an isoimide ring-closed polymer. Such imide ring closure and isoimide ring closure may be formed in the presence of a dehydration ring-closing catalyst such as dicyclohexylcarbodiimide, acetic anhydride, pyridine, trifluoroacetic anhydride, triethylamine, or may be thermally dehydrated by applying a temperature of 60 ° C to 200 ° C. It can be formed by ring closure. In particular, the use of a carbodiimide, acetic anhydride, or trifluoroacetic anhydride, which is a chemical ring-closing method, is preferable because the reaction rate can be easily controlled. The imide bond and the isoimide bond can be quantified by infrared absorption spectroscopy.

In the present invention, in order to further increase the sensitivity, benzoin tosylate, triphenylsulfonium triflate, diphenyliodohexafluoroantimonate, which is a compound that generates a Lewis acid upon irradiation with ultraviolet rays, is added to the polymer component. 0.1 to 10% by weight can be added.

Further, compounds which transfer to carboxylic acid upon irradiation with light, such as naphthoquinonediazidosulfonic acid ester, can be used in combination. Examples of such naphthoquinone diazide sulfonic acid ester compounds include compounds having a phenolic hydroxyl group such as polyhydroxybenzophenone, hydroquinone monomethyl ether, bisphenol A, pyrogallol, methyl gallic acid, and naphthol, to which naphthoquinone diazide sulfonic acid is ester-bonded. It can be used in an amount of 1 to 20% by weight based on the polymer component.

These photosensitive heat-resistant polymer precursors are synthesized by the following method. That is, a hydroxydiamino compound is dissolved in a polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, gamma-butyrolactone, and a tertiary amine such as triethylamine, an epoxy compound such as propylene oxide, dihydropyran, and the like. By reacting dicarboxylic acid dichloride in the presence of the above unsaturated cyclic ether compound, the polymer of the general formula (1) can be synthesized. Also,
Hydroxydiamino compounds and diamine compounds are represented by N-methyl-2-pyrrolidone, N, N-dimethylacetamide,
By reacting the corresponding tetracarboxylic dianhydride, hydroxytetracarboxylic dianhydride or the like in a polar solvent such as gamma-butyrolactone, general formulas (2) and (3)
Can be synthesized. Further, tetracarboxylic dianhydride and hydroxytetracarboxylic dianhydride are mixed with alcohols such as methanol and ethanol and pyridine in a polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide and gamma-butyrolactone. By reacting in the presence of an amine catalyst such as triethylamine to synthesize the corresponding dicarboxylic acid diester, and in the presence of a dehydration condensing agent such as dicyclohexylcarbodiimide, a hydroxydiamino compound or a diamino compound is reacted to obtain a general formula. Polymers (2) and (3) can be obtained.

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

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, a titanium chelating agent, etc. 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, 3-aminopropyltrimethoxysilane, etc., a titanium chelating agent, or an aluminum chelating agent is 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, etc. 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. Substrates include silicon wafers, ceramics,
Gallium arsenide is used, but is not limited thereto. As a coating method, there are methods such as spin coating, spray coating, and roll coating. The thickness of the coating varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like.
It is applied so that it becomes.

Next, the substrate coated with the photosensitive composition is dried to obtain a photosensitive composition film. Drying is preferably performed using an oven, hot plate, infrared ray, etc., at a temperature of 50 ° C to 150 ° C 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 heat-resistant polymer precursor pattern is achieved by removing the exposed portion using a developer after exposure. As a developing solution, an aqueous solution of tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol Dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like, and an aqueous solution of a compound exhibiting alkalinity are preferred. In some cases, these alkaline aqueous solutions are added with N
-Methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, polar solvents such as dimethylacrylamide, alcohols such as methanol, ethanol, isopropanol, ethyl lactate, propylene glycol Esters such as monomethyl ether acetate and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be added alone or in combination of several kinds. After development, it is rinsed with water. Here, rinsing treatment may be performed by adding alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and acids such as acetic acid and carbonic acid to 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 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 ° C., 200 ° C., and 350 ° C. 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 by 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.

[0047]

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

Method for Measuring Characteristics Measurement of Film Thickness The thickness of the photosensitive heat-resistant resin precursor 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. It was measured.

Measurement of Sensitivity A varnish of photosensitive polyimide was baked on a 6-inch silicon wafer at 80 ° C. × 3 minutes + 100 ° C. × 3 minutes and then heated to 10 μm to SCW-636 manufactured by Dainippon Screen Co., Ltd. And spin coated. After application,
350 on SCW-636 4 inch silicon wafer
Spin coating was performed so that the film thickness after the heat treatment at 10 degrees became 10 microns. This is a GCW i-line stepper DSW
Using -8000, an exposure dose of 50 mJ / cm ² (10
0 msec) to 1500 mJ / cm ² (3000 ms)
Exposure processing was performed at a focus of 0 μm at intervals of 25 mJ / cm ² (50 msec) until ec).

After the exposure, the wafer was immersed in the developing solutions described in Examples and Comparative Examples to perform development. The development time is 15
The time at which the portion exposed at 00 mJ / cm ² dissolved was 1.
Five times later. After this development, the exposure amount at which the exposed portion was completely dissolved was defined as the sensitivity. When the sensitivity is 400 mJ / cm ² or more, the exposure time per wafer becomes too long, so that the production efficiency decreases and the sensitivity becomes 100 mJ / c.
If it is less than m ^2, it becomes difficult to accurately control the exposure amount, and thus a problem often occurs in the reproducibility of the pattern.

Measurement of Organic Solvent Resistance After pre-baking on a 4-inch silicon wafer at 100 ° C. for 3 minutes on a hot plate of Dainippon Screen SCW-636 using a coater part of a coater developer SCW-636 made by Dainippon Screen. Thickness of 10μm ±
A spin-coated film was formed to a thickness of 1 μm, and was prebaked under the above conditions.

This film was treated with a 0.5% aqueous solution of tetramethylammonium hydroxide for 30 seconds, and then rinsed with ultrapure water for 1 minute.

The wafer was placed in an inert oven INH-15 manufactured by Koyo Lindberg Co. at 100 ° C. for 10 minutes,
Heat treatment was performed at 0 ° C. for 30 minutes and then at 350 ° C. for 1 hour in nitrogen (oxygen concentration: 20 ppm or less).

One drop of N-methyl-2-pyrrolidone (NMP) was dropped on the film after the heat treatment, and heated at 200 ° C. for 3 minutes in an inert oven DT-43 manufactured by Yamato Scientific Co., Ltd.
The situation around the dropping of P was visually observed. When the organic solvent resistance is poor, cracks and traces of dissolution are observed around the area where NMP is dropped.

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

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 solution temperature was raised to 40 ° C, and 5-naphthoquinonediazidosulfonyl chloride was added.
8 g (0.1 mol) was added and stirred. Next, a solution of 10.1 g (0.1 mol) of triethylamine dissolved in 20 g of gamma-butyrolactone was added dropwise to this solution so that the temperature of the reaction solution did not exceed 45 ° C. After dropping, 40 ° C
For 2 hours. The urea compound and salt precipitated from this solution were removed by filtration, and the filtrate was poured into 5 l of 1% aqueous acetic acid to form a precipitate of polyhydroxyamidate polyamidate having naphthoquinonediazidosulfonyl group bonded thereto. 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 was dissolved in 30 g of GBL to obtain a varnish A of a photosensitive heat-resistant resin precursor composition having a viscosity at 25 ° C. of 1 Pa · s.

This was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH).
Further, development was possible even with a 0.6% aqueous solution of TMAH or a 5% aqueous solution of TMAH. This sensitivity is 250mJ / c
m ^2, which was very good, and the film loss of the unexposed portion after development was as good as 0.5 μm. There were no problems such as cracks in organic solvent resistance.

Example 2 18.3 g (0.05 mol) of BAHF under a stream of dry nitrogen
Was dissolved in 50 ml of dimethylacetamide and cooled to -10 ° C. Here 34.8 g of glycidyl methyl ether
(0.6 mol) was added. To this solution, a solution in which 11 g (0.054 mol) of isophthalic acid dichloride was dissolved in 30 ml of tetrahydrofuran was added dropwise over 20 minutes. After the completion of the dropwise addition, the reaction was carried out at -10 ° C for 1 hour, and then stirring was continued at 20 ° C for 6 hours.

Thereafter, the temperature of the solution was raised to 40 ° C.
26.8 g of naphthoquinonediazidosulfonyl chloride
(0.1 mol) was added and stirred. A solution obtained by dissolving 10.1 g (0.1 mol) of triethylamine in 20 ml of dimethylacetamide was added to this solution at a temperature of 40 ° C.
It was dropped so as not to exceed. After completion of the dropwise addition, stirring was continued at 40 ° C. for 2 hours.

After completion of the reaction, the resulting solution was poured into 10 l of water to obtain a polymer precipitate. Further, the polymer which was sufficiently washed with water and filtered was dried with a vacuum drier at 100 ° C. for 20 hours to obtain a photosensitive polymer solid.

10 g of this polymer was dissolved in 30 g of GBL to obtain a varnish B of a photosensitive heat-resistant resin precursor composition having a viscosity of 0.5 Pa · s at 25 ° C. 2.3.
Development was possible with an 8% TMAH aqueous solution. 0.6% more
Can be developed even with a 5% aqueous TMAH solution. This sensitivity was as good as 200 mJ / cm ^2, and the film loss after development was as good as 0.6 μm.
There were no problems such as cracks in organic solvent resistance.

Comparative Example 1 18.3 g (0.05 mol) of BAHF under a stream of dry nitrogen
Was dissolved in 50 ml of N-methyl-2-pyrrolidone (NMP). Here, 22.2 g (0.05 mol) of 4- (hexafluoroisopropylidene) diphthalic acid was added to NMP.
The mixture was added together with 20 ml, and stirring was continued at 25 ° C. for 2 hours and then at 40 ° C. for 3 hours. Thereafter, the solution was brought to 30 ° C., and 15.3 g (0.15 mol) of acetic anhydride and 23.7 of pyridine were added.
g (0.3 mol) in 50 ml of NMP
Dropped over minutes. The reaction was continued at 30 ° C. for 10 hours. After the completion of the reaction, the mixture was poured into 5 l of water to obtain a polyimide precipitate. After collecting the precipitate by filtration and washing well with water,
Drying was performed for 20 hours using a vacuum dryer at 100 ° C.

10 g of this polymer was dissolved in 50 g of gamma-butyrolactone, and 6.9 g (0.025 mol) of 5-naphthoquinonediazidosulfonyl chloride was added to give 40 g.
° C. Here, 2.5 g of triethylamine (0.02
(5 mol) was added dropwise to 10 g of gamma-butyrolactone so that the reaction temperature did not exceed 45 ° C. After completion of the dropwise addition, stirring was continued at 40 ° C. for 2 hours.

Thereafter, the resultant was poured into 10 l of water to obtain a soluble polyimide solid having a naphthoquinonediazidosulfonyl group introduced into a hydroxyl group. This solid was dried in a vacuum dryer at 60 ° C. for 20 hours.

10 g of this polymer was dissolved in 30 g of NMP to obtain a varnish C of a photosensitive heat-resistant resin precursor composition. Development was not possible with 0.6% and 2.38% TMAH aqueous solution. The sensitivity is 300 mJ / cm ² ,
Although the film loss of the unexposed portion was 0.3 μm, the organic solvent resistance was poor, and the area around which NMP was dropped was dissolved and cracks occurred.

Comparative Example 2 18.3 g (0.05 mol) of BAHF under a stream of dry nitrogen
Was dissolved in 50 ml of N-methyl-2-pyrrolidone (NMP). Here, 22.2 g (0.05 mol) of 4- (hexafluoroisopropylidene) diphthalic acid was added to NMP.
The mixture was added together with 20 ml, and stirring was continued at 25 ° C. for 2 hours and then at 40 ° C. for 3 hours.

2,3,4,100 g of this polymer solution
Of 4 hydroxyl groups of 4'-tetrahydroxybenzophenone, 5 g of a compound obtained by esterifying 1.5 hydroxyl groups (4NT-150 manufactured by Toyo Gosei Co., Ltd.) was added and stirred to obtain a varnish of a positive photosensitive polyimide. Was.

In the development of the varnish, development was possible with a 0.6% TMAH aqueous solution, but it took a very long time. 2.3
When development was carried out with an 8% TMAH aqueous solution, the film loss of the unexposed portion was as large as 7 μm. Sensitivity is 300mJ / cm
^Although it was ² , the organic solvent resistance was poor, and the area around which NMP was dropped dissolved and cracks occurred.

Comparative Example 3 18.3 g (0.05 mol) of BAHF under a stream of dry nitrogen
Was dissolved in 50 ml of N-methyl-2-pyrrolidone (NMP). Here, 22.2 g (0.05 mol) of 4- (hexafluoroisopropylidene) diphthalic acid was added to NMP.
The mixture was added together with 20 ml, and stirring was continued at 25 ° C. for 2 hours and then at 40 ° C. for 3 hours.

To 100 g of this polymer solution, 2, 3, 4,
Among 4 hydroxyl groups of 4'-tetrahydroxybenzophenone, 5 g of a compound obtained by esterification of 3.8 (4NT-380 manufactured by Toyo Gosei Co., Ltd.) was added and stirred to obtain a varnish of a positive photosensitive polyimide. Was.

The varnish could not be developed with a 0.6% TMAH aqueous solution. 2.38% TMAH aqueous solution and 5% TMAH aqueous solution were able to develop,
The sensitivity was as low as 450 mJ / cm ^2, and the film reduction was 1 μm. In addition, the organic solvent resistance was poor, and the area around which NMP was dropped dissolved and cracks occurred.

[0073]

According to the present invention, it is possible to obtain a positive photosensitive heat-resistant resin precursor composition which can be developed with a wide range of aqueous alkaline solutions, has high sensitivity, and has little film loss in unexposed areas. .

Claims (6)

[Claims] 1. A photosensitive heat-resistant resin precursor composition comprising a polymer represented by the general formula (1). Embedded image (Wherein, R1 is a divalent organic group having 2 to 30 carbon atoms,
R2 is a trivalent to hexavalent organic group having 6 to 40 carbon atoms,
R3 contains at least 10 to 50 mol% of a naphthoquinonediazidosulfonyl group, the rest being hydrogen atoms, n is an integer from 10 to 100,000, and p is an integer from 1 to 4. ) 2. A photosensitive heat-resistant resin precursor composition comprising a polymer represented by the general formula (2). Embedded image (Wherein, R4 is a trivalent or tetravalent organic group having 2 to 30 carbon atoms, R5 is a trivalent to hexavalent organic group having 6 to 40 carbon atoms, R6 is a hydrogen atom or a 1 to 20 carbon atoms. 1
R7 contains a naphthoquinonediazidosulfonyl group in at least 10 to 50 mol% of the whole, the remainder is a hydrogen atom, m is an integer from 10 to 10000, q is 1 or 2, and r is 1 to 3 It is an integer. ) 3. A photosensitive heat-resistant resin precursor composition comprising a polymer represented by the general formula (3). Embedded image (Wherein, R8 contains at least 10 to 50 mol% of a naphthoquinonediazidosulfonyl group, the remainder is a hydrogen atom, R9 is a tetra- to octavalent organic group containing at least 6 carbon atoms, and R10 is at least 2 A divalent group having a carbon atom, R11 is hydrogen or an organic group having 1 to 20 carbon atoms, a is an integer from 10 to 10,000, s is an integer from 1 to 4, and t is 1 or 2.) 4. The polymer represented by the general formula (1), (2) or (3), wherein the diamine having a silicon atom in the R2, R5 and R10 components is 1 to 2 of the R2, R5 and R7 components.
The photosensitive heat-resistant resin precursor composition according to any one of claims 1 to 3, which is contained in an amount of 0 mol%. 5. A polymer represented by the general formula (1), (2) or (3), wherein the compound represented by the general formula (4) is contained in an amount of 1 to 50 parts by weight based on 100 parts by weight of the polymer. The photosensitive heat-resistant resin precursor composition according to claim 1. Embedded image (Wherein, R12 is a trivalent or tetravalent having 2 to 30 carbon atoms)
5 to 30 mol% of the valence organic group R13 is a divalent group containing a silicon atom and having 4 to 20 carbon atoms,
70 to 95 mol% of 3 represents a divalent organic group having 2 to 30 carbon atoms. R14 is a hydrogen atom and / or a monovalent organic group having 1 to 20 carbon atoms, b is 1 to 100
An integer up to 00, u is 1 or 2. ) 6. A polymer represented by the general formula (1), (2) or (3), wherein 1 to 50 parts by weight of the compound represented by the general formula (5) is contained in 100 parts by weight of the polymer. The photosensitive heat-resistant resin precursor composition according to claim 1. Embedded image (R15 is a tetravalent organic group having 2 to 30 carbon atoms, R1
6 to 5 to 30 mol% of carbon atoms containing silicon atoms
From 30 to 30 divalent groups, 70 to 95 mol% of R16
Is a divalent organic group having 2 to 30 carbon atoms. c is an integer from 1 to 10,000. )