JP2000338668A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure high sensitivity and resolution and to obtain a resin layer excellent in heat resistance by incorporating a cis-diene substituted polyamic acid having a specified structure unit or a polyimide and an oxygen sensitizer. SOLUTION: The photosensitive resin composition contains a cis-diene substituted polyamic acid having a structural unit of the formula or a polyimide and an oxygen sensitizer. In the formula, at least one of R1-R4 is a monovalent organic group having a cis-diene structure, the remainders are each H, hydroxy, carboxyl, a 1-20C alkyl or a 1-20C alkoxyl, X1 and X2 are each O, S, a 1-4C alkylene or a 1-4C alkyleneoxy, Ar1 and Ar2 are each a divalent aromatic group, l1, l2, m1 and m2 are each 0 or 1, where when l1 is 1, m1 is also 1, and when l2 is 1, m2 is also 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a photosensitive resin composition. More specifically, the present invention can be applied to the production of semiconductor elements and circuit wiring boards, etc., and has a high sensitivity and resolution, and a negative photosensitive resin composition capable of obtaining a resin layer having excellent heat resistance. About things.

[0002]

2. Description of the Related Art In recent years, electronic devices have become lighter, thinner, shorter and more sophisticated due to their portability. Along with this,
Semiconductor devices are becoming smaller and more highly integrated. For example, the reliability of semiconductor circuits formed on a semiconductor chip has been improved due to the advancement of circuit miniaturization due to the high integration of the circuit itself and the miniaturization of the package size, and the thinner package encapsulant that protects the chip. It is common to use a protective film such as a passivation film on a circuit on a chip surface. In addition, the circuit has been multi-staged via an interlayer insulating film for higher integration. On the other hand, a ball grid array (BGA) and a chip scale
Package (CSP), Multi-chip module (M
New packaging technologies that realize high-density packaging such as CM) have been developed. These semiconductor packages use a substrate made of various materials such as plastics and ceramics called an interposer to electrically connect electrodes of a semiconductor chip to a printed wiring board. The circuit formed on the substrate is introduced into a miniaturized semiconductor, and has become much thinner and more dense than a general printed wiring board. Therefore, it is necessary to protect the fine wiring depending on the type of the package. Furthermore, in printed circuit boards on which these semiconductor packages are mounted, new technologies such as a build-up method, in which an insulating resin is interposed on a base material to gradually form a wiring layer, are used to increase the wiring density. Is being developed. Common requirements for these protective resins or interlayer insulating resins are high heat resistance that can withstand high temperatures of 200 to 300 ° C. during chip bonding and mounting, and conduction between wiring joints and insulating layers. In particular, the interposer protective film and the interlayer insulating film for build-up circuit boards that require processing on the substrate have low processability at a low temperature that does not damage the substrate during processing. No. Conventionally, polyimide resin is used for applications such as protective films on semiconductor chips that require heat resistance, and epoxy resin is used for protective films and interlayer insulating films, especially on circuit substrates that require low-temperature processability. I was Further, in order to perform pattern processing of holes and the like corresponding to the circuit wiring of high density, it is advantageous to form them by photoengraving (photography), that is, to use a photosensitive resin obtained by imparting photosensitivity to these resins. is there. As for the polyimide resin, a polyimide having such photosensitivity, so-called photosensitive polyimide, has been developed (for example, Japanese Patent Publication No. 55-30207, Japanese Patent Application Laid-Open No. 54-14579).
No. 4 gazette). These photosensitive polyimides generally form a crosslinked structure by photo-radical polymerization of methacrylate introduced into the carboxyl group of a polyamic acid that is a precursor thereof, and use the difference in solubility with an uncrosslinked portion in a developer. We perform pattern processing such as holes. When such a polyamic acid is converted to a polyimide, methacrylate forming a bond with a carboxyl group must be eliminated, and stronger heating is required as compared with the conventional ring-closing imidization of a polyamic acid. Moreover, the methacrylate structure that has been eliminated remains in the polyimide, which greatly reduces properties such as heat resistance and mechanical properties.
It is necessary to decompose and evaporate the detached methacrylate structure at a high temperature. For this reason, such a photosensitive polyimide needs to be processed at a higher temperature than a normal polyimide resin. In order to improve such high-temperature processing, there has been proposed a resin in which an acrylate structure is introduced into a side chain of a previously closed polyimide to realize low-temperature processing (for example, JP-A-59-108031). After processing, the acrylate structure will remain in the resin as it is,
The properties such as heat resistance are inferior. As for the epoxy resin, various photosensitive epoxy resins have been put into practical use as a solder resist for protecting circuit wiring and a resin for interlayer insulation for build-up. However, none of them sufficiently satisfies properties such as heat resistance and flexibility for following the deformation of the base material which is thinned by thinning the package. As a photosensitive material composition suitable as a high-resolution and high-sensitivity resist, there has been proposed a photosensitive material composition comprising a fullerene having no photosensitive group and a photosensitive agent such as a diazide compound (Japanese Patent No. 2814174). However, since this composition is composed of fullerene and a low molecular weight diazide compound, the viscosity of the solution is low, and it is difficult to apply the composition uniformly by spin coating while maintaining the required thickness. The strength and heat resistance of a film formed by polymerization and cross-linking of a diazide compound having a molecular weight are low, and furthermore, there is an economic problem that, at present, an extremely expensive fullerene is compounded at least 5 times the weight of the diazide compound.

[0003]

The present invention can be applied to the production of semiconductor elements, circuit wiring boards, and the like, and can provide a negative-type resin layer having high sensitivity, high resolution, and excellent heat resistance. The purpose of the present invention is to provide a photosensitive resin composition.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, oxygen-enriched cis-diene-substituted polyamic acid or polyimide having a specific molecular structure in the side chain has been obtained. By blending a sensitizer, especially fullerene, it has been found that a photosensitive resin composition having significantly improved sensitivity, resolution and heat resistance can be obtained as compared with the conventional heat-resistant photosensitive resin. The present invention has been completed. That is, the present invention provides (1) a photosensitive resin composition comprising: a cis-diene-substituted polyamic acid or polyimide having a structural unit represented by the general formula [1]; and an oxygen sensitizer.

Embedded image (Wherein, at least one of R ¹ , R ² , R ³ and R ⁴
One is a monovalent organic group having a cis-diene structure, and the rest is each independently hydrogen, a hydroxyl group, a carboxyl group, an alkyl group having 1 to 20 carbon atoms, or a carbon atom having 1 to 2 carbon atoms.
X ¹ and X ² are each independently oxygen, sulfur or an alkylene group or an alkyleneoxy group which may have a substituent having 1 to 4 carbon atoms;
Ar ¹ and Ar ² are each independently a divalent aromatic group, and l ₁ , l ₂ , m ₁ and m ₂ are each independently 0 or 1. However, when l ₁ is 1, m ₁ is also 1, and when l ₂ is 1, m ₂ is also 1. ), (2) a photosensitive resin composition comprising a cis-diene-substituted polyamic acid or polyimide having a structural unit represented by the general formula [2] and an oxygen sensitizer;

Embedded image (Where R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R
^At least one of ¹¹ and R ¹² is a monovalent organic group having a cis-diene structure, and the rest is each independently hydrogen,
A hydroxyl group, a carboxyl group, an alkyl group having 1 to 20 carbon atoms or an alkoxyl group having 1 to 20 carbon atoms,
Y ¹ is oxygen, sulfur or an alkylene group, an alkylidene group or an alkyleneoxy group which may have a substituent having 1 to 4 carbon atoms, and n ₁ is 0 or 1. (3) The photosensitive resin composition according to (1) or (2), wherein the cis-diene structure is a furan, thiophene or pyrrole structure, and (4) the oxygen sensitizer is a fullerene. An object of the present invention is to provide a certain photosensitive resin composition according to the above (1), (2) or (3).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION First of the photosensitive resin composition of the present invention.
Is a ci having a structural unit represented by the general formula [1]
It contains an s-diene-substituted polyamic acid or polyimide and an oxygen sensitizer.

Embedded image However, in the general formula [1], R ¹ , R ² , R ³ and R ⁴
At least one is a monovalent organic group having a cis-diene structure, and the rest is each independently hydrogen, a hydroxyl group, a carboxyl group, an alkyl group having 1 to 20 carbon atoms or an alkoxyl group having 1 to 20 carbon atoms. X ¹ and X ²
Are each independently oxygen, sulfur or an alkylene group or an alkyleneoxy group which may have a substituent having 1 to 4 carbon atoms, and Ar ¹ and Ar ² are each independently a divalent aromatic group. , L ₁ , l ₂ , m ₁ and m ₂ are each independently 0 or 1. However, when l ₁ is 1, m ₁ is also 1, and when l ₂ is 1, m ₂ is also 1.

A second embodiment of the photosensitive resin composition of the present invention comprises a cis-diene-substituted polyamic acid or polyimide having a structural unit represented by the general formula [2] and an oxygen sensitizer. .

Embedded image However, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R
^At least one of ¹² is a monovalent organic group having a cis-diene structure, and the rest is each independently hydrogen, a hydroxyl group, a carboxyl group, an alkyl group having 1 to 20 carbon atoms or an alkoxyl group having 1 to 20 carbon atoms. Y ¹ is oxygen, sulfur or an alkylene group, an alkylidene group or an alkyleneoxy group which may have a substituent having 1 to 4 carbon atoms, and n ₁ is 0 or 1. Note that an atom such as halogen which replaces hydrogen is also a substituent. In the composition of the present invention, the cis-diene-substituted polyamic acid or polyimide having a structural unit represented by the general formula [1] or [2] is substituted with a monovalent organic group having a cis-diene structure. It is characterized in that the main chain is bonded to the meta position of the aromatic ring. When the main chain is bonded to the para position of the aromatic ring,
Molecular packing such as crystallinity of polyamic acid or polyimide tends to increase, and particularly, solubility in a developing solution in a state where a cis-diene structure is introduced is reduced. As a result, at the time of creating a light pattern, the difference in the dissolution rate in the developing solution between the unexposed portion, which should be originally dissolved in the developing solution, and the exposed portion, which has been photo-crosslinked, is less likely to be manifested. Is required, a resin pattern of a good shape is hardly obtained, and the resin in an unexposed portion is hardly completely removed. As in the composition of the present invention, if a bond to the main chain is present at the meta position of the aromatic ring substituted with a monovalent organic group having a cis-diene structure, the corresponding polyamic acid and the developing solution of the polyimide Improved solubility,
As a result, the contrast between the exposed part and the unexposed part becomes clear, and the optical patterning property is improved.

In the composition of the present invention, only one kind of the structural unit represented by the general formula [1] or [2] may be present in the polyamic acid or the polyimide, and two or more types may be copolymerized. It may be present as a unit. In the composition of the present invention, the cis-diene-substituted polyamic acid or polyimide having the structural unit represented by the general formula [1] or the general formula [2] may contain only one kind, or two or more kinds. They may be mixed and contained. Further, the composition of the present invention comprises a cis-diene-substituted polyamic acid or polyimide having a structural unit represented by the general formula [1] or [2] and a general formula [1] or a general formula [2]. And a mixture with a polyamic acid or polyimide having no structural unit. In the general formula [1] and general formula [2], the monovalent organic group having a cis- diene structure, for _{example, -CH 2 O-CO-D} , -O-CO-D,
_{-CO-O-CH 2 -D,} -CH 2 O-CH 2 -D, -O
_{-CH 2 -D, -NH-CO-} D, -CO-NH-CH 2
-D and the like. Where D is cis-
It has a diene structure. Examples of the cis-diene structure represented by D include a cyclopentadienyl group, a furyl group, a pyrrolyl group, a thienyl group, a pyranyl group, an isobenzofuranyl group, an indolizinyl group, and a quinolizinyl group. Among these, a cyclopentadienyl group, a furyl group, a pyrrolyl group and a thienyl group are particularly preferred. In the general formulas [1] and [2], the number of carbon atoms is 1
Examples of the alkyl group to -20 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group and a lauryl group. Among these, a methyl group, an ethyl group, a butyl group and a pentyl group are particularly preferred. In the general formulas [1] and [2], examples of the alkoxyl group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a lauryloxy group, and an isopropyloxy group. And the like. Among these, a methoxy group, an ethoxy group, a butoxy group and a pentyloxy group are particularly preferred.

Examples of the structural unit represented by the general formula [1] having these functional groups include the following formulas [1- (1)] to
The structural unit represented by [1- (20)] can be mentioned, and examples of the structural unit represented by the general formula [2] include formulas [2- (1)] to [2- (10)]. ] Can be mentioned.

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Embedded image The method for producing the cis-diene-substituted polyamic acid or polyimide having the structural unit represented by the general formula [1] or the general formula [2] used in the composition of the present invention is not particularly limited. After reacting a polycarboxylic dianhydride, a compound having a cis-diene structure
A divalent organic group can be introduced, or a diamine having a monovalent organic group having a cis-diene structure can be reacted with a polycarboxylic dianhydride. In the present invention, there is no particular limitation on the polycarboxylic dianhydride to be reacted with the diamine, for example, pyromellitic dianhydride,
3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-hexafluoroisopropylidene diphthalic anhydride And the like. Among these, 4,4′-hexafluoroisopropylidene diphthalic anhydride can be particularly preferably used.

[0009] A monovalent organic group having a cis-diene structure is introduced into a polyamic acid or polyimide obtained by polymerizing a diamine having no cis-diene structure and having no monovalent organic group with a polycarboxylic dianhydride. In this case, a diamine represented by the general formula [3] or [4] and a polycarboxylic dianhydride can be used as starting materials.

Embedded image However, in the general formula [3], R ¹³ , R ¹⁴ , R ¹⁵ , R
^At least one of ¹⁶ is a hydroxyl group, a hydroxymethyl group or a carboxyl group, and the remainder is each independently hydrogen, an alkyl group having 1 to 20 carbon atoms or a carbon atom having 1 to 2 carbon atoms.
0 is an alkoxyl group, X ³ and X ⁴ are each independently oxygen, sulfur or an alkylene group or an alkyleneoxy group which may have a substituent having 1 to 4 carbon atoms;
Ar ³ and Ar ⁴ are each independently a divalent aromatic group, and l ₃ , l ₄ , m ₃ and m ₄ are each independently 0 or 1. However, when l ₃ is 1, m ₃ is also 1, and when l ₄ is 1, m ₄ is also 1. In the general formula [4], R
^At least one of R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ is a hydroxyl group, a hydroxymethyl group or a carboxyl group; An alkyl group having 1 to 20 carbon atoms or an alkoxyl group having 1 to 20 carbon atoms, and Y ² is oxygen, sulfur or 1 carbon atom.
To 4 substituents alkylene group which may have a an alkylidene group or alkyleneoxy group, n ₂ is 0
Or 1. Note that an atom such as halogen which replaces hydrogen is also a substituent. Examples of the diamine represented by the general formula [3] include 3,5-diaminobenzyl alcohol, 3,5-diaminophenol, and 3,5-diaminobenzoic acid. As the diamine represented by the general formula [4], for example, 3,3′-diamino-4,
4'-dihydroxybiphenyl, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3,5-bis (4-aminophenoxy) benzyl alcohol and the like can be mentioned.

In the present invention, the method of reacting the diamine represented by the general formula [3] or [4] with the polycarboxylic dianhydride is not particularly limited, and the polyamic acid is synthesized by a known polymerization method. be able to. For example, by reacting a diamine represented by the general formula [3] with pyromellitic dianhydride in a solvent such as N-methyl-2-pyrrolidone to have a structural unit represented by the general formula [5] A polyamic acid can be obtained. further,
By subjecting the polyamic acid having the structural unit represented by the general formula [5] to a dehydration ring-closing reaction, a polyimide having the structural unit represented by the general formula [6] can be obtained.

Embedded image The method is particularly limited to a method of introducing a monovalent organic group having a cis-diene structure into a polyamic acid having a structural unit represented by the general formula [5] or a polyimide having a structural unit represented by the general formula [6]. For example, by reacting a halide having a cis-diene structure in the presence of a base, a polyamic acid having a structural unit represented by the general formula [5] or a structure represented by the general formula [6] A monovalent organic group having a cis-diene structure can be introduced into the hydroxyl group of the polyimide having units. When R ¹⁵ in the general formula [5] is a hydroxyl group and the halide having a cis-diene structure is furfuryl bromide, a polyamic acid having a structural unit represented by the general formula [7] is obtained. .

Embedded image

In the present invention, when a polyamic acid or polyimide is synthesized by reacting a diamine having a monovalent organic group having a cis-diene structure with a polycarboxylic acid dianhydride, a cis-diene structure that can be used is synthesized. Examples of the diamine having a monovalent organic group include, for example,
3,5-diaminobenzyl-2-furoate, 1,1,1,1,
3,3,3-hexafluoro-2,2-bis (4-furfuryloxy-3-aminophenyl) propane, 3,3′-diamino-4,4′-di (2-furoylamino) biphenyl,
4,4'-difurfuryloxy-3,3'-diaminobiphenyl and the like can be mentioned. These diamines
For example, by reacting an aromatic dinitro compound having a hydroxyl group, a carboxyl group or a hydroxyalkyl group with a halide having a cis-diene structure such as furfuryl bromide in the presence of a base, and subsequently reducing the nitro group, Obtainable. The method for reducing the nitro group is not particularly limited, and examples thereof include reduction with hydrazine, catalytic hydrogenation in the presence of a transition metal catalyst such as nickel, palladium, and platinum, and reduction with an indium-ammonium chloride aqueous solution. The cis-diene-substituted polyamic acid or polyimide having a structural unit represented by the general formula [1] or [2] used in the present invention is soluble in a solvent or an aqueous alkaline solution. This polyamic acid or polyimide easily reacts with singlet oxygen generated by the action of the oxygen sensitizer to form a polyamic acid or polyimide intermediate having a peracid group. This intermediate immediately reacts with the adjacent polyamic acid or polyimide, crosslinks each other by polycondensation, and dramatically increases the molecular weight. Thereby, the polyamic acid or the polyimide becomes insoluble. Further, the heat resistance of the polyamic acid or polyimide crosslinked by the polycondensation reaction is dramatically increased. Unlike the conventional photosensitive polyimide, the photosensitive resin composition of the present invention is crosslinked by polycondensation of the cis-diene structure with singlet oxygen, not by photoradical polymerization. Is not hindered, and the heat resistance of the obtained crosslinked resin is excellent.

In the present invention, the molecular weight of the cis-diene-substituted polyamic acid or polyimide having a structural unit represented by the general formula [1] or [2] is preferably 5,000 or more, and 000 to 1,000,000
00, more preferably 50,000 to 200,
More preferably, 000. If the molecular weight of the polyamic acid or polyimide is too small, it may be difficult to obtain a uniform film. If the molecular weight of the polyamic acid or polyimide is too large, the solubility may decrease, and it may be difficult to form a uniform film. The oxygen sensitizer used in the composition of the present invention is not particularly limited, but is preferably an oxygen sensitizer having an excited triplet energy of 22.5 kcal / mol or more. Examples of such an oxygen sensitizer include methylene blue, rose bengal, hematoporphyrin, tetraphenylporphine, rubrene, fullerene C60, fullerene C70, fullerene C82, and the like. One of these oxygen sensitizers can be used alone, or two or more can be used in combination. Among these,
Fullerene C60 and fullerene C70 can be particularly preferably used. In the composition of the present invention, the amount of the oxygen sensitizer is not particularly limited, but 100 parts by weight of a cis-diene-substituted polyamic acid or a polyimide having a structural unit represented by the general formula [1] or the general formula [2]. 0.0 per
It is preferably from 1 to 20 parts by weight, more preferably from 0.1 to 10 parts by weight. If the amount of the oxygen sensitizer is too small, the sensitizing effect may be insufficient.
If the amount of the oxygen sensitizer is too large, not only is it economically disadvantageous, but also it may be difficult to form a uniform film. The composition of the present invention containing a high molecular weight cis-diene-substituted polyamic acid or polyimide and an oxygen sensitizer has an appropriate viscosity when used as a solution, and maintains a required film thickness on a silicon wafer by spin coating. It can be applied uniformly. Further, since a film is formed by crosslinking the high molecular weight cis-diene-substituted polyamic acid or polyimide in the composition, the film is excellent in strength and heat resistance. Further, since an expensive oxygen sensitizer such as fullerene is used in a relatively small amount, it can be produced economically advantageously.

The method of using the photosensitive resin composition of the present invention is not particularly limited, but generally, after forming a coating film on a substrate / substrate and performing pattern processing by exposure and development, If necessary, thermosetting is further performed to form a resin layer. There is no particular limitation on the method of forming the coating film.For example, a varnish obtained by dissolving a photosensitive resin composition in a solvent is directly applied on a substrate / substrate by spin coating or the like, and then dried under mild conditions. Or a varnish obtained by dissolving in a solvent is applied in advance to a release substrate made of a plastic sheet or a metal such as stainless steel, and the coating obtained by drying under mild conditions is applied to the substrate / substrate. And a method of transferring by laminating under pressure. The wavelength of light used for exposure of the composition of the present invention can be appropriately selected according to the oxygen sensitizer used. For example, when fullerene C60 is used as a sensitizer, light in a wide wavelength range (250 to 780 nm) from the ultraviolet region to the visible light region can be used. The exposure can be performed by irradiating the resin layer with light through a mask that can shield a portion of the formed resin layer from which the resin is to be removed. Development after exposure can be performed using an organic solvent or an alkaline aqueous solution that dissolves the unexposed resin composition. The resin in the exposed portion is insolubilized by the reaction, but the resin in the unexposed portion is dissolved. As a result, the resin can be subjected to pattern processing such as holes using a mask. The cis-diene-substituted polyamic acid having a structural unit represented by the general formula [1] or [2] can be thermally cured after development, and the polyamic acid can be converted to a polyimide by a dehydration ring closure reaction. The conditions of the thermosetting reaction are not particularly limited, but are usually 150 to 250 ° C.
For 30 minutes or more. Heating is hot air,
Infrared irradiation, on a hot plate, etc. Usually, it can be carried out in an air atmosphere, but if necessary, it can be carried out in an atmosphere of an inert gas such as nitrogen or carbon dioxide, or under reduced pressure. The cis-diene-substituted polyimide does not necessarily need to undergo a thermosetting reaction, but by heating under the above temperature conditions, a high heat history is given to the resin, and the heat resistance can be further improved. By using the resin composition of the present invention in these processing steps, a pattern-formed resin layer having excellent heat resistance is formed by processing at a low temperature, and a semiconductor element, a printed circuit wiring board, and the like having good characteristics. Can be manufactured.

[0014]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. Example 1 8.47 g (0.0392 mol) of 3,3'-diamino-4,4'-dihydroxybiphenyl and 8.55 g (0.0392 mol) of pyromellitic anhydride in 50 ml of N-methyl-2-pyrrolidone The mixture was stirred at 60 ° C. to obtain a solution of polyamic acid. On the other hand, 5.00 g (0.0510 mol) of furfuryl alcohol was dissolved in 50 ml of tetrahydrofuran,
While maintaining the temperature at 0 ° C., 4.90 g of phosphorus tribromide (0.0181 g)
Mol) was added dropwise. After stirring for about 2 hours, add water and add
The organic component was extracted twice using 00 ml of ether. The ether layer was washed with sodium hydrogen carbonate, 30 g of molecular sieve was added, dried overnight, and filtered to obtain an ether solution of furfuryl bromide. The obtained solution was analyzed by FT-IR, ¹ H-NMR and ¹³ C-NMR, and it was confirmed that the solution was furfuryl bromide. Next, 150 ml of N-methyl-2-pyrrolidone was added to the above solution of the polyamic acid to dilute the solution, and an ether solution containing 7.70 g of furfuryl bromide and 6.50 g of potassium carbonate were added. Stirred.
Next, resolidification precipitation treatment was performed using methanol, and the precipitate was dried under vacuum to obtain 16.3 g of a polyamic acid having a structural unit represented by the formula [2- (10)]. ^{As a} result of analysis by ¹ H-NMR, 80 mol% of the diamine structural units in the polyamic acid were substituted by furfuryl groups. The molecular weight of this polyamic acid was about 70,000. High purity fullerene C6
0 [99.98% by weight, manufactured by Term Co.] 0.75 g and the above furfuryl group partially substituted polyamic acid 10.0 g,
γ-butyrolactone / 1,1,2,2-tetrachloroethane (70/30, volume ratio) was dissolved in 50 ml to obtain a homogeneous solution. This solution was filtered through a filter having a pore size of 0.1 μm, applied to a silicon wafer by spin coating, and dried by heating at 80 ° C. for 10 minutes to form a thin film having a thickness of 2 μm. The thin film is exposed to light through a photomask (topographic test chart) using a 500 W ultra-high pressure mercury lamp, and immediately immersed in a 10 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds to perform a developing process. Was completely dissolved and removed to form a resin pattern having a line width of 5 μm or less. The obtained resin pattern was heated at 200 ° C. for 1 hour to form a resin layer. For this resin layer, room temperature to 3
The TG / DTA device [TG / DTA220, manufactured by Seiko Denshi Kogyo Co., Ltd., temperature rise rate 1
0 ° C./min] was 0.3% by weight.

Example 2 14.36 g (0.0392 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane
And 8.55 g (0.0392 mol) of pyromellitic dianhydride were stirred at 60 ° C. in 50 ml of N-methyl-2-pyrrolidone to obtain a polyamic acid solution. Next, N-methyl-2-pyrrolidone 15 was added to the polyamic acid solution.
The mixture was diluted by adding 0 ml, and an ether solution containing 7.70 g of furfuryl bromide and 6.50 g of potassium carbonate were added, followed by stirring at 80 ° C. for about 2 hours. Next, re-coagulation-precipitation treatment was performed using methanol, and the precipitate was dried under vacuum to obtain 20.3 g of a polyamic acid having a structural unit represented by the formula [2- (5)]. ^{As a} result of analysis by ¹ H-NMR, 80 mol% of the diamine structural units in the polyamic acid were substituted by furfuryl groups. The molecular weight of this polyamic acid was about 50,000. High purity fullerene C60 [99.98% by weight,
Termm] 0.75 g and the above furfuryl group partially substituted polyamic acid 10.0 g were mixed with γ-butyrolactone / 1,
1,2,2-tetrachloroethane (70/30, volume ratio)
Dissolved in 50 ml to make a homogeneous solution. This solution was filtered through a filter having a pore size of 0.1 μm, and then applied on a silicon wafer by a spin coating method.
By heating and drying for 0 minutes, a thin film having a thickness of 2 μm was formed. The thin film is exposed to light with a 500 W ultra-high pressure mercury lamp through a photomask, immediately immersed in a 10 wt% aqueous solution of TMAH for 30 seconds and developed to completely dissolve and remove the unexposed portion, thereby obtaining a resin having a line width of 5 μm or less. A pattern was formed. The obtained resin pattern is heated at 200 ° C. for 1 hour.
By heating for a time, a resin layer was formed. About this resin layer, when the thermogravimetric reduction rate from room temperature to 300 ° C. was measured with a TG / DTA apparatus in the same manner as in Example 1,
It was 0.5% by weight.

Comparative Example 1 The procedure of Example 1 was repeated, except that 8.47 g (0.0392 mol) of 4,4'-diamino-3,3'-dihydroxybiphenyl was used as the diamine component to partially substitute a furfuryl group. The synthesized polyamic acid was synthesized. ^{As a} result of analysis by ¹ H-NMR, 85 mol% of the diamine structural units in the polyamic acid were substituted by furfuryl groups.
The molecular weight of this polyamic acid was about 80,000. 0.75 g of high-purity fullerene C60 [99.98% by weight, manufactured by Term Co.] and 10.0 g of the above partially substituted furfuryl group-substituted polyamic acid were combined with γ-butyrolactone / 1,1,2,2-tetrachloroethane (70/30). (Volume ratio: 50 ml) to obtain a uniform solution. This solution was filtered through a filter having a pore size of 0.1 μm, and then applied on a silicon wafer by a spin coating method.
By heating and drying at 10 ° C. for 10 minutes, a thin film having a thickness of 2 μm was formed. This thin film is put through a photomask for 50 minutes.
Exposure with 0W ultra-high pressure mercury lamp, immediately 10% by weight TM
The developing treatment was performed by immersion in the AH aqueous solution, but the residue in the unexposed portion was not completely removed even after immersion for 1 minute or more.

Reference Example 1 (3,5-diaminobenzyl-2)
Preparation of furoate) Preparation of 3,5-dinitrobenzyl-2-furoate: 3,5-dinitrobenzyl alcohol 37 in a 500 ml separable flask equipped with a stirrer, water-cooled reflux condenser, thermometer and dropping funnel. 0.0 g was dissolved in 100 ml of pyridine. While cooling to 0 to 5 ° C, 53.1 g of 2-furoyl chloride was added dropwise. After the dropwise addition, the reaction solution was returned to room temperature and stirred for 2 hours. 400 ml of water was added and the solid was filtered. The obtained solid was mixed with ethyl alcohol / water (80 /
20, volume ratio) to obtain 47 g of 3,5-dinitrobenzyl-2-furoate. 86% yield. Melting point 1
16.0-117.7 ° C. 3,5-diaminobenzyl-2
Preparation of furoate: 14.6 g of 3,5-dinitrobenzyl-2-furoate were dissolved in 120 ml of ethyl acetate and 80 ml of ethyl alcohol in a 1 liter separable flask equipped with a stirrer and a water-cooled reflux condenser. After adding 120 ml of a saturated aqueous solution of ammonium chloride, 100 g of indium metal powder was added. The mixture was stirred under reflux for 17 hours to perform a reduction reaction. After completion of the reaction, the reaction solution was transferred to a 2 liter beaker, 1 liter of water was added, and the solid was filtered off. The pH of the filtrate was adjusted to 9 with a 2N aqueous sodium hydroxide solution, followed by extraction with ethyl acetate. The ethyl acetate layer was dried over magnesium sulfate. Ethyl acetate was distilled off under reduced pressure to obtain 10 g of a crude product. The crude product was purified by silica gel column chromatography to obtain 4.6 g of 3,5-diaminobenzyl-2-furoate. Yield 4
0%. Recrystallized from ethyl alcohol, melting point 119-1
Acicular crystals at 21.1 ° C. were obtained. Further, the same synthesis and purification were repeated twice.

EXAMPLE 3 9.09 g (0.0392 mol) of 3,5-diaminobenzyl-2-furoate synthesized in Reference Example 1 and 17.4 g of 4,4'-hexafluoroisopropylidene diphthalic anhydride
1 g (0.0392 mol) of γ-butyrolactone in 50 ml
The mixture was stirred at room temperature in a medium to obtain a solution of a polyamic acid having a structural unit represented by the formula [1- (1)]. This solution contains N
-Methyl-2-pyrrolidone (50 ml) for dilution,
The polyamic acid was coagulated and precipitated by pouring into methanol (75/25, volume ratio), followed by filtration and vacuum drying to obtain a light yellow powder of the polyamic acid having a structural unit represented by the formula [1- (1)]. 9 g were obtained. 0.75 g of high-purity fullerene C60 [99.98% by weight, manufactured by Term Co.]
And 10.0 g of the above-mentioned floyl group-substituted polyamic acid with γ
-Butyrolactone / 1,1,2,2-tetrachloroethane (70/30, volume ratio) was dissolved in 50 ml to obtain a homogeneous solution. This solution was filtered through a filter having a pore size of 0.1 μm, applied to a silicon wafer by spin coating, and dried by heating at 80 ° C. for 10 minutes to form a thin film having a thickness of 2 μm. The thin film is exposed to light with a 500 W ultra-high pressure mercury lamp through a photomask, immediately immersed in a 10 wt% aqueous solution of TMAH for 30 seconds and developed to completely dissolve and remove the unexposed portion, thereby obtaining a resin having a line width of 5 μm or less. A pattern was formed. The obtained resin pattern was heated at 200 ° C. for 1 hour to form a resin layer. The thermogravimetric reduction rate of this resin layer from room temperature to 300 ° C. was 0.3% by weight.

Reference Example 2 (Production of 3,3'-diamino-4,4'-di-2-furoylaminobiphenyl) 3,3'-dinitro-4,4'-di-2-furoylaminobiphenyl Preparation of 3,3′-dinitro-4,4′-diaminobiphenyl 1 in a 500 ml separable flask equipped with a stirrer, water-cooled reflux condenser, thermometer and dropping funnel.
After dissolving 0.96 g in 200 ml of N, N-dimethylformamide, 20 ml of pyridine was added. While cooling to 13 to 14 ° C, 12.53 g of 2-furoyl chloride was added dropwise. After completion of the dropwise addition, the reaction solution was returned to room temperature, and stirring was continued for 5 hours. 80 ml of 2N hydrochloric acid and then 100 ml of water were added, and the solid was filtered. The solid was washed well with water and dried under reduced pressure to obtain 15.0 g of 3,3'-dinitro-4,4'-di-2-furoylaminobiphenyl. Yield 81%. 3,3 '
-Preparation of diamino-4,4'-di-2-furoylaminobiphenyl: 3,3'-dinitro-4,4'-di-in a separable flask equipped with a stirrer and a water-cooled reflux condenser. 2
-Furoylaminobiphenyl 7.4 g, N-methyl-2
100 ml of pyrrolidone and 75 ml of ethyl alcohol were charged. After adding 40 ml of a saturated aqueous solution of ammonium chloride, 25.6 g of indium metal powder was added, and the mixture was stirred at 80 ° C. for 1 hour. After cooling the reaction solution to room temperature,
The solid was filtered off. The filtrate was concentrated to about 1/2 under reduced pressure, 300 ml of water was added, and the precipitated solid was filtered to obtain 2.9 g of a crude product. The crude product was purified by silica gel column chromatography and 3,3'-diamino-4,4 '
1.5 g of di-2-furoylaminobiphenyl were obtained.
23% isolated yield. Recrystallization from N-methyl-2-pyrrolidone / ethyl acetate (25/75, volume ratio) gave a decomposition point of 25.
Acicular crystals at 6-259 ° C were obtained. Further, the same synthesis and purification were repeated 12 times.

Example 4 3,3′-Diamino-4,4′-di-2 synthesized in Reference Example 2
15.76 g (0.0392 g) of furoylaminobiphenyl
Mol) and 17.41 g (0.0392 mol) of 4,4'-hexafluoroisopropylidene diphthalic anhydride were stirred at room temperature in 50 ml of γ-butyrolactone to obtain a compound of the formula [2- (1)]
A solution of a polyamic acid having a structural unit represented by the following formula was obtained. This solution was diluted by adding 50 ml of N-methyl-2-pyrrolidone, poured into water / methanol (75/25, volume ratio) to coagulate and precipitate polyamic acid, and filtered and vacuum-dried to give a pale yellow powder. 31.5 g of a polyamic acid having a structural unit represented by [2- (1)] was obtained.
High purity fullerene C60 [99.98% by weight, Ter
m) and 10.0 g of the above-mentioned furoyl group-substituted polyamic acid in γ-butyrolactone / toluene (60
/ 40, volume ratio) to obtain a homogeneous solution.
This solution was filtered through a filter having a pore size of 0.1 μm, applied to a silicon wafer by spin coating, and dried by heating at 80 ° C. for 10 minutes to form a thin film having a thickness of 2 μm. This thin film was exposed through a photomask with a 500 W ultra-high pressure mercury lamp, and immediately
The unexposed portion was completely dissolved and removed by immersing in a 30 wt% aqueous solution of TMAH for 30 seconds to carry out a developing treatment, and the line width was 5 μm.
The following resin pattern was formed. The obtained resin pattern was heated at 200 ° C. for 1 hour to form a resin layer. The thermogravimetric reduction rate of this resin layer from room temperature to 300 ° C. was 0.2% by weight.

[0021]

The photosensitive resin composition of the present invention has excellent performance as a heat-resistant negative photoresist. The polyamic acid or polyimide used in the composition of the present invention is originally soluble in a solvent such as an aqueous alkaline solution,
Singlet oxygen generated from an oxygen sensitizer such as 60 causes the cis-diene group in the side chain to undergo oxidative polycondensation, crosslink, and become insoluble in the solvent. Accordingly, a negative-type pattern that can be used with high sensitivity and high resolution, which cannot be achieved by the conventional heat-resistant photoresist composition, can be obtained. In particular, when fullerene is used as the oxygen sensitizer, the heat resistance of the resin layer after pattern formation is significantly improved.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Right Deputy Tajima 2-1 Hirosawa, Wako City, Saitama Prefecture Inside RIKEN (72) Inventor Kazuo Takeuchi 2-1 Hirosawa Wako City, Saitama Prefecture Inside RIKEN (72 Inventor Etsu Takeuchi 2-5-8 Higashishinagawa, Shinagawa-ku, Tokyo F-term in Sumitomo Bakelite Co., Ltd. SA01 SA06 SA31 SA49 SA62 SA64 SA71 SA72 SA73 SA77 SA81 SB01 SB02 TA01 TA22 TB01 TB02 UA121 UA122 UA131 UA132 UA662 UA672 UB011 UB061 UB121 UB131 UB281 UB401 UB402 VA021 VA022 VA051 VA061 VA062 VA081 YB19 YB07Y18B18B

Claims (4)

[Claims] 1. It has a structural unit represented by the general formula [1].
A photosensitive resin composition comprising a cis-diene-substituted polyamic acid or polyimide and an oxygen sensitizer. Embedded image (Wherein, at least one of R ¹ , R ² , R ³ and R ⁴
One is a monovalent organic group having a cis-diene structure, and the rest is each independently hydrogen, a hydroxyl group, a carboxyl group, an alkyl group having 1 to 20 carbon atoms, or a carbon atom having 1 to 2 carbon atoms.
X ¹ and X ² are each independently oxygen, sulfur or an alkylene group or an alkyleneoxy group which may have a substituent having 1 to 4 carbon atoms;
Ar ¹ and Ar ² are each independently a divalent aromatic group, and l ₁ , l ₂ , m ₁ and m ₂ are each independently 0 or 1. However, when l ₁ is 1, m ₁ is also 1, and when l ₂ is 1, m ₂ is also 1. ) 2. It has a structural unit represented by the general formula [2].
A photosensitive resin composition comprising a cis-diene-substituted polyamic acid or polyimide and an oxygen sensitizer. Embedded image (Where R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R
^At least one of ¹¹ and R ¹² is a monovalent organic group having a cis-diene structure, and the rest is each independently hydrogen,
A hydroxyl group, a carboxyl group, an alkyl group having 1 to 20 carbon atoms or an alkoxyl group having 1 to 20 carbon atoms,
Y ¹ is oxygen, sulfur or an alkylene group, an alkylidene group or an alkyleneoxy group which may have a substituent having 1 to 4 carbon atoms, and n ₁ is 0 or 1. ) 3. The photosensitive resin composition according to claim 1, wherein the cis-diene structure is a furan, thiophene or pyrrole structure. 4. The photosensitive resin composition according to claim 1, wherein the oxygen sensitizer is fullerene.