JPH11202489A - Photosensitive heat resistant resin precursor composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a positive type photosensitive heat resistant resin precursor compsn. developable with an aq. alkali soln. and excellent in sensitivity even in a large film thickness. SOLUTION: The photosensitive heat resistant resin precursor compsn. contains a polymer represented by the formula and a compd. which generates a Lewis acid under UV and/or radiation. In the formula, R1 is a 2-30C divalent org. group, R2 is 6-40C tri- to hexavalent org. group, R3 is a monovalent org. group which is converted to a hydroxyl group when dissociated in the presence of an acid and is a 3-20C alkoxycarbonyl group, (n) is an integer of 10-100,000 and (p) is an integer of 1-4. The compsn. can form a pattern with slight exposure even in a large final film thickness of about 10 μm and a film of the compsn. after heat treatment is excellent in solvent resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a photosensitive composition useful as a surface protective film for semiconductors, in particular, it can be developed with an aqueous developing solution and has a high sensitivity and good pattern even when the film thickness is as thick as 10 .mu.m. The present invention relates to a positive photosensitive resin precursor composition that can be formed.

[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.

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. Polyamide resin having a hydroxyl group to which naphthoquinonediazide is added also has a limitation in the structure in order to obtain solubility, and when the final film thickness is 10 μm or more, light absorption by the polymer film is increased. In addition, since the number of naphthoquinonediazidosulfonic acid ester molecules that need to cause a photoreaction increases, the required exposure dose increases. For this reason, there is a problem that the sensitivity is reduced, the time required for exposure processing of one wafer is enormous, and the production efficiency is reduced.

[0004] In addition, a photoresist compound whose sensitivity has been drastically increased by changing the solubility of a polymer by a chemical reaction with a compound which generates an acid by ultraviolet light and the acid is known as Ito.
(H. Itoh and CGWillso
n, Polymer Engineering Science 23, 101
2 (1983)). However, the polymer described here is a very heat-resistant resin such as polyhydroxystyrene, and although it may be used as a photoresist, it is a protective film for LSI that needs heat resistance to leave the film permanently. It could not be used for such purposes.

[0005] In addition, a photosensitive polyimide obtained by adding a photoacid generator to a soluble polyimide in which a phenolic hydroxyl group of a soluble polyimide having a special structure is protected by a t-butoxycarbonyl group (t-BOC group) is used. (Table, Yamaoka, Nitto Giho, Vol. 28 (No. 2), 3)
7, (1990)). However, since such a polyimide resin is soluble in an organic solvent, when it is used for a protective film of an LSI or the like, the solvent resistance of the film is poor, so that the fatal dissolution of the film in the process is fatal. There was a problem.

In view of the above drawbacks, the present inventors have found that adding a photoacid generator to a polyamide acid ester having a hydroxyl group protected by an organic group or a polyamide having a hydroxyl group protected by an organic group. It has been found that the acid generated in the light-irradiated portion removes the organic group protecting the hydroxyl group and becomes soluble in the alkali developing solution. Further, by causing a cyclization reaction by a heat treatment, the film can be made to have solvent resistance. Further, they have found that since the quantum yield of this photoreaction exceeds 1, a large change occurs with a small amount of exposure, and thus the sensitivity can be remarkably improved, leading to the present invention.

[0007]

A positive photosensitive heat-resistant resin that can form a pattern with a small exposure dose and has excellent solvent resistance in a heat-treated film even when the final film thickness is as thick as about 10 μm. It is intended to provide a precursor composition.

[0008]

The present invention is characterized in that it contains (a) a polymer represented by the general formula (1) and (b) a compound which generates a Lewis acid by ultraviolet light and / or radiation. This is a photosensitive heat-resistant resin precursor composition.

[0009]

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 is a monovalent organic group which becomes a hydroxyl group by dissociation in the presence of an acid, an alkoxycarbonyl group having 2 to 20 carbon atoms, n is an integer of 10 to 100,000, and p is an integer of 1 to 4 . )

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The polymer represented by the general formula (1) in the present invention can be a polymer that forms an oxazole ring by heating or an appropriate catalyst.

In the above 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 6 to 30 carbon atoms. Specific examples include, but are not limited to, phthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, dicarboxydiphenylhexafluoropropane, dicarboxydiphenylpropane, benzophenonedicarboxylic acid, and diphenylsulfonedicarboxylic acid. In addition, an aliphatic dicarboxylic acid such as adipic acid, oxalic acid, or cyclohexanedicarboxylic acid can be copolymerized within a range in which the heat resistance and the solvent resistance of the obtained heat-resistant resin are not problematic. The copolymerization amount of such an aliphatic dicarboxylic acid is preferably 1 to 30 mol% of the acid component. 30
If the amount is more than mol%, the heat resistance of the obtained film is lowered, which is not preferable.

In the above general 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, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 4,4'-dihydroxy-3,
3'-diaminodiphenyl sulfone, 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-diaminopyrimidine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-hydroxytriazine and the like are protected by R3. Can be mentioned.

In the range of 1 to 30 mol% of the diamine component, hydroxyl-free paraphenylenediamine, bis (trifluoromethyl) benzidine, dimethylbenzidine, diaminodiphenyl ether, diaminodiphenylsulfone, bis (aminophenoxy) benzene, Aromatic diamines such as bis (aminophenoxyphenyl) hexafluoropropane, bis (aminophenoxyphenyl) sulfone and bis (aminophenoxyphenyl) propane; or aliphatic diamines such as ethylenediamine, hexamethylenediamine, cyclohexyldiamine, methylenebiscyclohexylamine 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.

R3 in the general formula (1) represents a compound which undergoes an elimination reaction by an acid generated by irradiation with ultraviolet rays or the like and is converted into a hydroxyl group. For this example,
A t-butoxycarbonyl group is particularly preferred, and an alkoxycarbonyl group having 2 to 20 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a phenoxycarbonyl group, and a benzyloxycarbonyl group is also preferred.

In the present invention, the polymer represented by the general formula (2) can be a polymer which 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-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 formula (2), R7 can be the same as R3 in the general formula (1).

In formula (3), the same R8 as R3 in formula (1) can be used.

In the general formula (3), R9 represents a carboxylic acid component having a protected hydroxyl group, and preferred are those having a structure represented by the following formula.

[0022]

Embedded image In the formula, R17 and R19 are a trivalent or tetravalent organic group having 2 to 30 carbon atoms, R18 is a trivalent to hexavalent organic group having 2 to 30 carbon atoms, R20 and R22 are a hydrogen atom, and / or
Or a monovalent organic group having 1 to 20 carbon atoms, R21 is a monovalent organic group which dissociates into a hydroxyl group in the presence of an acid,
t-butoxycarbonyl group, phenoxycarbonyl group,
Benzyloxycarbonyl group, methoxycarbonyl group,
An alkoxycarbonyl group having 3 to 20 carbon atoms such as an ethoxycarbonyl group, v and x represent 1 or 2, and w represents an integer of 1 to 4. The structure of a specific compound is shown in the following formula.

[0023]

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, and methylenebiscyclohexylamine, and R4 in the general formula (2) can be used.

In the general formula (4), R11 represents a carboxylic acid component, and the same as R4 in the general formula (2) can be used.

In the general formula (4), R12 has a divalent group having from 4 to 30 carbon atoms containing a silicon atom in an amount of 5 to 30 mol% of its constituent components, and other than that, has a carbon number of 2 to 30. 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 general formula (4), R13 can be the same as R6 in the general formula (2).

The general formula (5) represents a structure represented by the general formula (4) in which the imide is closed, and R15
Represents an imide-ring-closed compound having the structure represented by R11 in the general formula (4). R16 is the same as R13 in the general formula (4).

The polymer in the general formulas (2) and (3) is heated in the presence of a dehydration ring-closing catalyst such as dicyclohexylcarbodiimide, acetic anhydride, pyridine, trifluoroacetic anhydride, triethylamine, or by applying a temperature of 60 to 200 ° C. An imide ring and an isoimide ring can be partially formed by dehydration and ring closure. It is preferable that such imide rings and isoimide rings account for 1 to 70% of the whole. If the amount exceeds this range, problems such as a decrease in solubility in an aqueous alkali solution and an increase in absorption, resulting in a decrease in sensitivity of the resulting photosensitive heat-resistant resin precursor composition occur.

In the present invention, it is preferable to include a fluorine atom for the purpose of improving the water repellency of such a polymer. However, when fluorine atoms are present in the polymer
When the content is 5% by weight or more, the solubility of the obtained polymer is improved, so that there is a problem that the chemical resistance is reduced. For this reason, it is preferable to add 5 to 25% by weight of fluorine atoms to the polymer of the present invention.

In the present invention, benzoin tosylate, 2- (4'-methoxystyryl) -4,
6-bis (trichloromethyl) -s-triazine, diphenyliodotrifluoromethanesulfate, triphenylsulfidehexafluoroantimonate, phthalimidyl triflate, phthalimidyl nitrobenzene sulfonate, naphthalimidyl tosylate, pyrogallol trimesylate And diphenyliodocamphorsulfonate, naphthoimidylcamphorsulfonate, naphthoimidyltriflate, and the like, and other substances that generate an acid by ultraviolet rays can also be used. Particularly, as the acid, those which generate sulfonic acids such as methanesulfonic acid, trifluoromethylmethanesulfonic acid, toluenesulfonic acid, nitrobenzenesulfonic acid, and camphorsulfonic acid are preferable.
These sulfonic acids are less susceptible to the amine component in the air because of their lower acidity than those called super strong acids such as hexafluoroantimonate, and can be obtained with excellent stability. .

Further, a compound such as naphthoquinonediazidesulfonic acid ester which transfers to carboxylic acid upon irradiation with light 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. Can be used.

These 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. Further, the hydroxydiamino compound and the diamine compound may be N-methyl-
By reacting the corresponding tetracarboxylic dianhydride, hydroxytetracarboxylic dianhydride or the like in a polar solvent such as 2-pyrrolidone, N, N-dimethylacetamide, gamma-butyrolactone, the 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 a corresponding dicarboxylic diester, and then reacting a hydroxydiamino compound or a diamino compound in the presence of a dehydrating condensing agent such as dicyclohexylcarbodiimide, the 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.

In order to further enhance the adhesion to the 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, 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 and 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. 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, a hot plate, infrared rays or the like 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 developing solution after 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 Aminoethyl methacrylate, cyclohexylamine,
An aqueous solution of an alkaline compound such as ethylenediamine or 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 may be added to these aqueous alkali solutions.
Alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone, alone or in combination. It may be added. 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 the 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 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.

[0045]

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

Measurement Method of Properties Measurement of Film Thickness The thickness of the photosensitive heat-resistant resin precursor composition at a refractive index of 1.64 was measured using an optical film thickness measuring device Lambda-ace STM-602 manufactured by Dainippon Screen Co., Ltd. Was measured.

Measurement of Sensitivity A varnish of a 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 by SCW-636 manufactured by Dainippon Screen Co., Ltd. And spin coated. After application,
350 on 4 inch silicon wafer of SCW-636
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 exposure, the wafer was subjected to a heat treatment at 110 ° C. for 1 minute on a SCW-636 hot plate, and then the wafer was immersed in the developing solutions described in Examples and Comparative Examples to perform development. The development time was 1.5 times as long as the time required for dissolving the portion exposed at 1500 mJ / cm ² . After this development, the exposure amount at which the exposed portion was completely dissolved was defined as the sensitivity. 400m sensitivity
If it is J / cm ² or more, the exposure time per wafer becomes too long, so that the production efficiency is reduced and the sensitivity becomes 1
When it is less than 00 mJ / cm ² , it is difficult to accurately control the exposure amount, so that a problem often occurs in pattern reproducibility.

Measurement of Resistance to Organic Solvent After pre-baking on a 4-inch silicon wafer at 100 ° C. for 3 minutes on a hot plate of SCW-636 manufactured by Dainippon Screen Co., Ltd. using a coater part of a coater developer SCW-636 manufactured by Dainippon Screen Co., Ltd. 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.

Synthesis Example 1 Synthesis of t-butoxycarbonylated dihydroxydiamine 18.3 g of (3-amino-4hydroxyphenyl) hexafluoropropane (BAHF) under a stream of dry nitrogen.
(0.05 mol) in 100 ml of tetrahydrofuran
Dissolve at 0 ° C. Here, potassium t-butoxide11.
2 g (0.1 mol) was added, and stirring was continued for 30 minutes to obtain a paste-like liquid. Further, t-butyl dicarbonate 24.
A solution of 0 g (0.11 mol) dissolved in 20 ml of tetrahydrofuran was added dropwise over 5 minutes. After dropping, 2
Stirring was continued at 0 ° C. for 3 hours. After completion of the stirring, 1% aqueous acetic acid 2
The resulting precipitate was collected, washed with pure water repeatedly, and recrystallized with ethanol.

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 completion of the reaction, the solution was cooled to 10 ° C and 16.8 g (0.15 mol) of potassium t-butoxide was added. After 30 minutes, 34.9 g of (t-butyl) dicarbonate
(0.16 mol), and reacted at 10 ° C. for 1 hour and then at room temperature for 3 hours.
3 was obtained with a polyhydroxyamidic ester protected with a t-butoxycarbonyl group. 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 produce a precipitate of protected polyhydroxyamic acid ester. This precipitate was collected, washed with water and methanol, and dried at 50 ° C. for 24 hours in a vacuum drier. The fluorine content of this polyhydroxyamic acid ester was 13.2% by weight, and the compounding amount of the silicon-containing diamine was 0% by mole.

A varnish A of a photosensitive heat-resistant resin precursor composition having a viscosity of 1 Pa · s at 25 ° C. obtained by dissolving 10 g of this polymer and 0.5 g of 1,8-naphthalimidyl triflate in 30 g of GBL. I got This had an imidation ratio of 5% and an isoimidation ratio of 10%.

It can be developed with a 2.38% aqueous solution of tetramethylammonium and has a sensitivity of 250 mJ / cm.
² and very good. There was no problem with 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, 7.5 g of potassium t-butoxide was obtained.
(0.067 mol) and stirring was continued for 20 minutes. Here, a solution in which 15.3 g (0.07 mol) of t-butyl dicarbonate was dissolved in 30 ml of tetrahydrofuran was added dropwise over 2 minutes. After completion of the dropwise addition, the reaction was continued at 20 ° C. for 3 hours.

After the completion of the reaction, the obtained solution was diluted with 1% aqueous acetic acid.
0 l to obtain a polymer precipitate. Further, the polymer, which was sufficiently washed with water and filtered, was dried in a vacuum drier at 100 ° C. for 2 hours.
After drying for 0 hour, a solid of polyhydroxyamide in which a part of hydroxyl groups was protected by t-butoxycarbonyl group was obtained.
The polyhydroxyamide has a fluorine atom content of 18.
The blending amount of 2% by weight and the silicon-containing diamine was 0% by mole.

10 g of this polymer and 0.5 g of 1,8-naphthalimidyl camphor sulfonate were added to GBL30
g of a photosensitive heat-resistant resin precursor composition having a viscosity of 0.5 Pa · s at 25 ° C. was obtained.

It can be developed with a 2.38% aqueous solution of tetramethylammonium and has a sensitivity of 200 mJ / cm.
² and very good. There was no problem with organic solvent resistance.

Example 3 16.98 g (0.03 mol) of a diamine in which the hydroxyl group of BAHF obtained in Synthesis Example 1 was protected with a t-butoxycarbonyl group was dissolved in 20 ml of GBL and cooled to -10 ° C.
Here, 13.94 g of glycidyl methyl ether (0.2
4 mol) was added.

12.63 g of trimellitic anhydride chloride
(0.06 mol) dissolved in 30 g of acetone was added dropwise over 20 minutes to the BAHF solution protected with the t-butoxycarbonyl group. After the completion of the dropwise addition, the reaction was carried out at -10 ° C for 1 hour. Subsequently, the temperature of the solution was raised to 20 ° C and stirring was continued for 30 minutes.

Here, 14.27 g (0.033 mol) of bis (4-aminophenoxyphenyl) sulfone and BA protected with the t-butoxycarbonyl group synthesized in Synthesis Example 1 were used.
11.32 g (0.02 mol) of HF and 1,3-bis (3
-Aminopropyl) tetramethyldisiloxane 1.74
g (0.007 mol) with 20 ml of GBL
Reaction at 20 ° C for 1 hour, followed by 3,3 ', 4,4'-
9.31 diphenyl ether tetracarboxylic dianhydride
g (0.03 mol) and 1 hour at 20 ° C., then 5
Stirring was continued at 0 ° C. for 4 hours.

After the completion of the reaction, the solution was poured into 10 l of water to obtain a precipitate of a polyhydroxyamidamic acid alternating copolymer in which hydroxyl groups were protected by t-butoxycarbonyl group. The precipitate was dried in a vacuum dryer at 80 ° C. for 20 hours. The fluorine atom content of this polymer was 9.5% by weight, and the blending amount of the silicon-containing diamine was 11.7% by mole in the diamine component.

10 g of the powder of the polyhydroxyamidamic acid alternating copolymer having hydroxyl groups protected by t-butoxycarbonyl group thus obtained, 0.3 g of PAI-101 manufactured by Midori Kagaku as a photoacid generator, naphthoquinone 4NT-300 1.5 manufactured by Toyo Gosei as a sulfonic acid ester
g in 20 ml of GBL to give a viscosity at 25 ° C. of 2.
Varnish C of a photosensitive heat-resistant resin precursor composition having a pressure of 0 Pa · s was obtained.

It can be developed with a 0.8% aqueous solution of tetramethylammonium and has a sensitivity of 300 mJ / cm.
^{Was 2} . There was no problem with 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 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.

After completion of the reaction, the obtained solution was poured into 10 l of water to obtain a polymer precipitate. 100 ° C
For 20 hours to obtain a solid of polyhydroxyamide. The fluorine atom content of this polymer was 23.0% by weight. The amount of the silicon-containing diamine was 0 mol%.

10 g of this polymer and 0.5 g of benzoin tosylate were dissolved in 30 g of GBL to obtain Varnish D of a photosensitive heat-resistant resin precursor composition having a viscosity at 25 ° C. of 0.8 Pa · s. As a result, a positive image could not be obtained.

Comparative Example 2 Solid 10 g of polyhydroxyamide synthesized in Comparative Example 1
2 g of 4NT-300 manufactured by Toyo Gosei as a naphthoquinonediazidesulfonic acid ester compound was added to GBL3.
The resultant was dissolved in 0 g to obtain a varnish E of a photosensitive heat-resistant resin precursor composition having a viscosity at 25 ° C. of 1.0 Pa · s.

This was developed with a 1.2% aqueous solution of tetramethylammonium, and the sensitivity was 450 mJ / cm ^2.
It turned out to be low.

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. 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 12 hours. After completion of the reaction, the reaction mixture was poured into 2 liters of 1% aqueous acetic acid to obtain a precipitate of soluble polyimide. The precipitate was collected by filtration, washed sufficiently with water, and dried with a vacuum dryer at 100 ° C. for 20 hours. The fluorine atom content of this polymer was 28.1% by weight. 0 mol% of silicon-containing diamine
Met.

10 g of this soluble polyimide powder and 0.5 g of pyrogallol tritosylate were dissolved in 30 g of NMP to obtain a varnish F of a photosensitive heat-resistant resin precursor composition. The sensitivity was 300 mJ / cm ² , but the organic solvent resistance was poor, and the area around which NMP was dropped dissolved and cracks occurred.

Comparative Example 4 To a polymer solution synthesized under the same conditions as in Example 3, 18.9 g (0.09 mol) of trifluoroacetic anhydride was added.
Stirring was continued at 30 ° C. for 10 hours. After completion of the stirring, the mixture was poured into 2 l of 1% aqueous acetic acid to obtain a precipitate of soluble polyisoimide. The precipitate is collected by filtration, washed thoroughly with water,
For 20 hours.

10 g of this polymer and 0.5 g of 1,8-naphthalimidyl camphor sulfonate were added to NMP 30
g) to obtain a varnish of the photosensitive heat-resistant resin precursor composition G. As a result, absorption of i-ray was large, and a good positive image could not be obtained.

[0078]

According to the present invention, it is possible to obtain a positive photosensitive heat-resistant resin precursor composition which can be developed with an environment-friendly alkaline aqueous solution and has excellent sensitivity even in a thick state.

Claims (9)

[Claims] 1. A photosensitive heat-resistant resin precursor comprising: (a) a polymer represented by the general formula (1); and (b) a compound capable of generating a Lewis acid by ultraviolet light and / or radiation. Body composition. 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 is a monovalent organic group which becomes a hydroxyl group by dissociation in the presence of an acid, an alkoxycarbonyl group having 2 to 20 carbon atoms, n is an integer of 10 to 100,000, and p is an integer of 1 to 4 . ) 2. A photosensitive heat-resistant resin precursor comprising: (a) a polymer represented by the general formula (2); and (b) a compound capable of generating a Lewis acid by ultraviolet light and / or radiation. Body composition. 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 is a monovalent organic group which dissociates in the presence of an acid to become a hydroxyl group, an alkoxycarbonyl group having 2 to 20 carbon atoms, m is an integer of 10 to 100,000, and q is 1 Or 2, r is an integer of 1 to 3. ) 3. A photosensitive heat-resistant resin precursor comprising: (a) a polymer represented by the general formula (3); and (b) a compound capable of generating a Lewis acid by ultraviolet light and / or radiation. Body composition. Embedded image (Wherein, R8 is a monovalent organic group that dissociates in the presence of an acid to become a hydroxyl group, an alkoxycarbonyl group having a prime number of 2 to 20, and R9 is a 4- to 8-valent organic group containing at least 6 carbon atoms. A group, R10 is a divalent group having at least 2 carbon atoms, R11 is hydrogen or an organic group having 1 to 20 carbon atoms, a is an integer of 10 to 100,000, s is an integer of 1 to 4, t is 1 Or 2.) 4. The polymer component represented by the general formulas (1), (2) and (3), wherein the polymer component contains 5 to 25% by weight of fluorine atoms. Photosensitive heat-resistant resin precursor composition. 5. A polymer represented by the general formulas (1), (2) and (3), wherein a diamine having no hydroxyl group and having a silicon atom in R2, R5 and R10 components is R2, R5 and R1.
The photosensitive heat-resistant resin precursor composition according to any one of claims 1 to 3, wherein the composition contains 1 to 20 mol% of the 0 component. 6. A polymer represented by the general formula (1), (2) or (3), wherein the polymer represented by the general formula (4) is contained in an amount of 1 to 50 parts by weight per 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 10
An integer up to 0000, u is 1 or 2. ) 7. 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 100,000. ) 8. The photosensitive material according to claim 1, wherein the Lewis acid generated by the compound generating a Lewis acid by ultraviolet light and / or radiation is a sulfonic acid having 1 to 20 carbon atoms. Heat-resistant resin precursor composition. 9. A photosensitive heat-resistant resin precursor composition comprising the compound according to claim 1 and a naphthoquinonediazidesulfonic acid ester compound.