JP2001092138A - Positive type photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type photosensitive resin composition having high sensitivity and high contrast and exhibiting excellent resolution even in the case of a thick film having >10 μm thickness. SOLUTION: The positive type photosensitive resin composition contains (a) a polyamide soluble in alkyline water and (b) a photosensitive diazoquinone compound of formula 2 as essential components. In the formula, Z is a tetravalent organic group, R1-R4 are each a monovalent organic group, (k) is 0 or 1, (r) to (u) are each 0 or 1-3, one of symbols Q stands for naphthoquinonediazidosulfonic acid and the remainders are H.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive resin composition having excellent light sensitivity and resolution and a method for producing a high heat-resistant relief structure using the same.

[0002]

2. Description of the Related Art Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like has been used for a surface protective film and an interlayer insulating film of a semiconductor element. This polyimide resin is generally provided in the form of a photosensitive polyimide precursor composition, which is coated, patterned by actinic rays,
By applying development, thermal imidization, etc., it is possible to easily form a heat-resistant film that has been finely processed, and it has the feature that the process can be significantly shortened compared to conventional non-photosensitive polyimide. I have.

However, in the developing step, it is necessary to use a large amount of an organic solvent such as N-methyl-2-pyrrolidone as a developing solution. Have been In response to this, various proposals have recently been made for heat-resistant photosensitive resin materials that can be developed with a dilute alkaline aqueous solution, similarly to photoresists.

[0004] Among them, an alkali water-soluble polyhydroxyamide, for example, a polybenzoxazole (PBO) precursor is used to convert a photoactive component (P) such as quinonediazide (NQD).
In recent years, attention has been paid to a method of using it in combination with AC).
(Japanese Patent Publication No. 1-46862, JP-A-63-9616)
See No. 2 publication. According to these methods, an organic solvent-developable polyimide precursor is obtained because excellent performance such as easy formation of a positive pattern, good storage stability, and the same thermosetting film characteristics as polyimide can be obtained. Is attracting attention as a promising alternative material. In addition, a combination of a polymer having a phenolic hydroxyl group introduced into the main chain and PAC (Japanese Patent Application Laid-Open No. H11-106651, etc.),
Polymer having phenolic hydroxyl group introduced into side chain and PAC
(For example, Japanese Patent No. 2890213) has been proposed.

[0005] However, there are still many problems in the patterning performance obtained by the methods disclosed so far. In the case of a photosensitive composition originally using NQD, by adding NQD to an alkali-soluble polymer, the ability to reduce the alkali solubility (dissolution inhibition) of the composition is developed, and the developer resistance of an unexposed portion is generated. . On the other hand, in the exposed area, NQD is converted into indene carboxylic acid and dissolved in the developer. This means that patterning is performed using the difference in alkali solubility between the exposed and unexposed areas.
In order to obtain patterning performance with high sensitivity and a high residual film ratio (high contrast), it is most important to select a PAC capable of sufficiently obtaining a difference in solubility between the two. That is, PAC
The solubility is extremely reduced by the addition of, the unexposed area has sufficient alkali developing solution resistance, while the exposed area is efficiently decomposed even by a small amount of light, high sensitivity to express sufficient alkali solubility PAC must be used. In order to improve this by a development process, there is a method of diluting 2.38% tetramethylammonium hydroxide (TMAH) which has been widely used as an alkaline developer, but in this case, a special developer is separately provided. You need to prepare it is not reasonable.

To solve this problem, various quinonediazide-based photosensitizers (PAC) have been studied.
For example, it has been proposed to use a PAC obtained by converting a hydroxybenzophenone-based or bisphenol-based compound into an NQD, which has been widely used in conventional photoresists. (JP-A-64-6947, JP-A-3-207
See No. 43 gazette. However, in these PACs,
When the composition is applied to the alkali-soluble polyamide used in the present invention, the alkali dissolution inhibiting ability of the composition is very weak, the contrast is hardly obtained, and the film thickness of the obtained pattern is extremely low, which is not practical.

In order to further improve this, studies have been made to increase the introduction rate of NQD in PAC, and to use phenol having a bulky group in order to increase the hydrophobicity of the phenol nucleus of PAC. (JP-A-9-302
No. 221, JP-A-9-321038, JP-A-8-123034 and the like. However, when these PACs are used, the contrast is slightly improved as compared with the PACs, but the patterning performance is still insufficient. This is particularly noticeable in the case of a thick film having a thickness exceeding 10 μm. That is, when the thickness of the coating film is increased, generally required exposure dose and development time are increased, which is not preferable for a semiconductor manufacturing process that emphasizes productivity.

Accordingly, even in the case of a thick film as described above, while maintaining the developer resistance of the unexposed portion at a high level,
P that can enhance alkali solubility even by short-time exposure
The application of AC has become essential. However,
At present, conventional PACs do not provide sufficient performance to solve these problems.

[0009]

SUMMARY OF THE INVENTION According to the present invention, a film having a thickness of 10
Even in the case of a thick film exceeding μm, high sensitivity, that is, a pattern loss after development is small even in patterning in a low exposure range, high contrast and excellent resolution are exhibited. An object of the present invention is to provide a positive photosensitive resin composition that can be developed even with .38% TMAH and a method for producing a high heat-resistant relief structure using the same.

[0010]

Means for Solving the Problems The present inventors have proposed a photosensitive agent (PA
Focusing on C), intensive studies were conducted to develop a composition that can be developed with a 2.38% TMAH developer and can exhibit high sensitivity and high resolution patterning performance even in a thick film. As a result, they have found that a PAC having a specific structure can satisfy the above characteristics, and have completed the present invention. That is, the present invention provides (a) 100 parts by weight of a polyamide having a repeating unit represented by the following general formula (1):

[0011]

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Wherein X 1 is a trivalent to hexavalent organic group having at least 2 or more carbon atoms, Y 1 is a tetravalent to octavalent organic group having at least 2 or more carbon atoms, R 1 is hydrogen, or An organic group having 1 to 10 carbon atoms, n is 2 to 10
An integer up to 00, m is 0 or an integer of 1 to 2, p and q are 0 or an integer of 1 to 4, provided that m, p and q are not simultaneously 0. (B) A positive photosensitive resin composition containing 1 to 100 parts by weight of a photosensitive diazoquinone compound represented by the following general formula (2) as an essential component.

[0013]

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(Wherein Z is a tetravalent organic group, R 1, R 2, R
3, R4 is a monovalent organic group, k is 0 or 1, r, s, t,
u is 0 or an integer of 1 to 3, at least one of Q is a group shown below, and the rest are hydrogen atoms. )

[0015]

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In the present invention, the positive photosensitive resin composition is applied to a substrate in the form of a layer or a film and exposed to actinic light through a mask or directly irradiated with light, electron beam or ion beam. Thereafter, the present invention also provides an invention relating to a method for manufacturing a high heat-resistant relief structure obtained by eluting or removing the exposed portion or the irradiated portion, and then sintering the relief structure obtained at that time. Hereinafter, the present invention will be described in detail.

The polyamide in the present invention is represented by the formula (1), and has a diamine having a structure of X1 (OH) p and Y1 (O
H) It consists of a dicarboxylic acid having a structure of q (COOR1) m. When this polyamide is heated at about 300 to 400 ° C., the ring is closed and the polyamide is converted to a heat-resistant resin called polyimide or polybenzoxazole. Examples of the diamine having the structure of X1 (OH) p of the polyamide (1) of the present invention include aromatic diamine, silicon diamine, and hydroxydiamine. Among them, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diamino Diphenyl ether,
3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylmethane,
4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylketone,
4,4′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 2,2′-bis (4-aminophenyl) propane, 2,2′-bis (4-aminophenyl) hexafluoropropane, 3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4-methyl-2,4-bis (4-aminophenyl) ) -1-Pentene, 4-methyl-2,4-bis (4-aminophenyl) -2-pentene, 1,4-bis (α, α-dimethyl-4-aminobenzyl) benzene, imino-di-p-phenylene Diamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-
Methyl-2,4-bis (4-aminophenyl) pentane, 5 (or 6) -amino-1- (4-aminophenyl) -1,3,3-trimethylindane, bis (p-aminophenyl) phosphine oxide, 4,4′-diaminoazobenzene, 4,4′-diaminodiphenylurea,

4,4'-bis (4-aminophenoxy)
Biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane,
2,2bis [4- (3-aminophenoxy) phenyl] benzophenone, 4,4′-bis (4-aminophenoxy) diphenylsulfone, 4,4′-bis [4- (α,
α-dimethyl-4-aminobenzyl) phenoxy] benzophenone, 4,4′-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] diphenylsulfone, 4,4′-diaminobiphenyl, 4,4 '-Diaminobenzophenone, phenylindanediamine, 3,
3′-dimethoxy-4,4′-diaminobiphenyl,
3,3′-dimethyl-4,4′-diaminobiphenyl,
o-Toluidine sulfone, 2,2-bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfide, 1,4- (4-aminophenoxyphenyl) Benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) anthracene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-di- (3 -Aminophenoxy) diphenylsulfone, 4,4'-diaminobenzanilide and the like, and the hydrogen atom of the aromatic nucleus of these aromatic diamines is a chlorine atom, a fluorine atom, a bromine atom, a methyl group,
Examples include compounds substituted with at least one substituent selected from the group consisting of a methoxy group, a cyano group, and a phenyl group.

Further, silicon diamine can be selected in order to enhance the adhesiveness to the base material.
Bis (4-aminophenyl) dimethylsilane, bis (4
-Aminophenyl) tetramethylsiloxane bis (p-
Aminophenyl) tetramethyldisiloxane, bis (γ
-Aminopropyl) tetramethyldisiloxane, 1,4
-Bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane and the like. Further, in order to increase the alkali solubility of the polymer, it is preferable to use a diamine having a hydroxy group. For example, X1 includes a bisaminophenol compound represented by the following formula, but is not limited thereto. Absent.

[0020]

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Wherein A: -CH2-, -O-, -S
-, -SO2-, -CO-, -NHCO-, -C (CF
3) 2-] As a particularly preferable example among these, X1 is a group selected from the following formula.

[0022]

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In the formula (1), Y1 (OH) q (COOR1) m is represented by the following formula:

[0024]

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(Wherein A is —CH 2 —, —O—, —S
-, -SO2-, -CO-, -NHCO-, -C (CF
3) a group selected from 2-) and the following formula,

[0026]

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(Wherein R 1 is the same as R 1 in the above formula (1))
And further groups selected from the following.

[0028]

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(Wherein R 1 is the same as above, X 3 is —CH 2
-, -O-, -S-, -SO2-, -CO-, -NHC
O-, -C (CF3) 2-, a single bond, and groups shown below)

[0030]

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(Wherein X 4 is a group selected from the following)

[0032]

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In the formula (1), R 1 represents hydrogen or an organic group having 1 to 20 carbon atoms. When R 1 is hydrogen, the alkali solubility of the polymer is improved, but the resulting photosensitive composition has Since the stability and the ability to inhibit dissolution with PAC decrease, it is preferable that the hydrogen content of all R1 is 50% or less. When R1 is an organic group, the stability of the obtained photosensitive composition and the ability to inhibit dissolution with PAC are improved, but alkali solubility is decreased. Therefore, as the organic group, a group having a phenolic hydroxyl group is preferable. In particular, when both p and q are 0 in the formula (1),
Required. Preferred examples of the organic group having a phenolic hydroxyl group include a 3-hydroxybenzyl group and a 3,5-dihydroxybenzyl group.

The polyamide used in the present invention includes:
In particular, a structure having a repeating unit represented by the formula (3) is particularly preferable in terms of excellent alkali solubility and excellent patterning characteristics under a thick film based thereon.

[0035]

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(In the formula, X2 is the bisaminophenol described in the above X1, and Y2 is the same as the above Y1.) Among them, Y2 is preferably a group selected from the following formulas.

[0037]

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In the polyamide having the repeating units represented by the above general formulas (1) and (3), sealing the terminal group with a specific organic group is also included in the scope of the present invention. Examples of such a sealing group include, for example, JP-A-5-1
Examples thereof include groups having an unsaturated bond as described in JP-A-97153, and when these groups are used, it is considered preferable because the mechanical properties (elongation) of a coating film obtained after heat curing are improved. . Preferred examples of such a sealing group include the following.

[0039]

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In the positive photosensitive resin composition of the present invention, it is important to use a photosensitive diazoquinone compound represented by the general formula (2).

[0041]

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(Wherein Z is a tetravalent organic group, R5, R6, R
7, R8 are each independently a monovalent organic group, k is 0 or 1, m, n, p, and q are each independently an integer of 0 or 1 to 3, and at least one of Q is a group shown below. And the rest are hydrogen atoms)

[0043]

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Here, the tetravalent organic group represented by Z includes:

[0045]

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And

[0047]

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Preferred examples are the above, and the latter group is particularly preferred in terms of sensitivity and residual film ratio. R1, R2, R3 and R4 are each independently a monovalent organic group, and among them, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a cyclohexyl group and the like are preferable. Specific examples of the photosensitive diazoquinone compound represented by the general formula (3) include, but are not limited to, the following.

[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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Of these, particularly preferred examples include the following.

[0056]

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In use, these may be used alone or in combination of two or more. polyamide
The compounding amount of the photosensitive diazoquinone compound (b) with respect to (a) is 1 to 100 parts by weight with respect to 100 parts by weight of the polyamide, and if the compounding amount is less than 1 part by weight, the optical patterning property of the resin becomes poor, Conversely, if it exceeds 100 parts by weight, the tensile elongation of the film formed after heat curing is significantly reduced. The following phenolic compounds can be added to the positive photosensitive resin composition of the present invention, if necessary, mainly to improve developability.

[0058]

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The positive photosensitive resin composition of the present invention may contain an additive such as a leveling agent or a silane coupling agent for improving the adhesion. In the present invention, these components are dissolved in a solvent and used in the form of a varnish. As the solvent used, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-
Monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate and the like are used alone or in combination.

The method of using the photosensitive resin composition of the present invention is as follows.
First, the composition is applied to a suitable support, for example, a silicon wafer, ceramic, or aluminum substrate. The coating method is performed by spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, or the like. Next, after pre-baking at 60 to 130 ° C. to dry the coating film, a desired pattern shape is irradiated with actinic radiation. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible rays, and the like can be used, and those having a wavelength of 200 to 500 nm are preferable. Next, a relief pattern is obtained by dissolving and removing the irradiated portion with a developer.

Examples of the developer used include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia; primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like Aqueous solutions of alkalis such as quaternary ammonium salts, and methanol,
An aqueous solution to which an appropriate amount of a water-soluble organic solvent such as alcohol such as ethanol or a surfactant is added can be suitably used.

As a developing method, a system such as spray, paddle, immersion, or ultrasonic wave can be used. Next, the relief pattern formed by development is rinsed. Distilled water is used as the rinsing liquid. Next, heat treatment is performed to form an oxazole ring, and a final pattern having excellent heat resistance is obtained. The photosensitive resin composition of the present invention is useful not only for semiconductor applications but also as an interlayer insulating film of a multilayer circuit, a cover coat of a flexible copper clad board, a solder resist film, a liquid crystal alignment film, and the like.

[0063]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail.

[0064]

Example 1 <Synthesis of polyamide> 183.1 parts by weight (0.5 mol) of 2,2-bis (3-amino-4hydroxyphenyl) hexafluoropropane and N-methyl were placed in a separable flask having a capacity of 3 L. -2-pyrrolidone (NM
P) 1100 parts by weight and pyridine 63.3 parts by weight (0.8 mol) were added and dissolved by stirring. To this, a solution prepared by dissolving 65.0 parts by weight (0.32 mol) of isophthaloyl chloride and 16.2 parts by weight (0.08 mol) of terephthaloyl chloride in 200 parts by weight of diethylene glycol dimethyl ether was added while cooling with water. Thereafter, the reaction was performed at room temperature for 2 hours. Next, 59.2 parts by weight (0.4 mol) of phthalic anhydride and 31.6 parts by weight (0.4 mol) of pyridine were added to the reaction solution, and the mixture was further reacted at room temperature for 12 hours, so that the terminal of phthalic anhydride was obtained. A polymer sealed with was synthesized.

Thereafter, the above reaction solution was added dropwise to 8 L of water under high-speed stirring to disperse and precipitate the polymer. The polymer was recovered, washed appropriately with water, dehydrated and dried in vacuo to obtain the desired polyamide. Further, when further purification of the polymer is required, it can be carried out by the following method. That is, the polymer obtained above was converted to gamma-butyrolactone (GB
After re-dissolving in L), this is treated with a cation exchange resin and an anion exchange resin, and the resulting solution is poured into ion-exchanged water, and the precipitated polymer is separated by filtration, washed with water, and dried under vacuum. Thus, a purified polymer can be obtained.

<Preparation of Positive-Type Photosensitive Resin Composition> 100 parts by weight of synthesized polyamide (A-1), 15 parts by weight of diazoquinone (Q-1) having a structure of the following formula, and 10 parts by weight of bisphenol F were added to 200 parts by weight of GBL. After dissolving in
The solution was filtered through a 0.2 μm filter to obtain a photosensitive resin composition. <Evaluation of Photosensitive Characteristics> The positive photosensitive resin composition was applied to a silicon wafer previously treated with an aminosilane coupling agent using a spin coater, and then dried at 120 ° C. for 4 minutes on a hot plate to form a film. A coating having a thickness of about 13 μm was obtained. The coating film is passed through a reticle with a test pattern using an i-line stepper (manufactured by Nikon) at 300 mJ / cm.
Exposure ² was performed. Next, this exposure film is applied to NMD manufactured by Tokyo Ohka.
-3 developer (2.38% TMAH aqueous solution)
The exposed portion was dissolved and removed by performing development for 2 seconds, and then rinsed with pure water for 30 seconds. As a result, a 5 μm pattern (via hole, line and space, etc.) was resolved by optical microscope observation, and it was confirmed that there was no residue and the pattern had a good shape. At this time, the residual film ratio (film thickness after development / film thickness before development) was 92%.

[0067]

Example 2 The photosensitive characteristics were evaluated in the same manner as in Example 1 except that the diazoquinone compound in Example 1 was changed to the formula (Q-2).

[0068]

Example 3 Photosensitivity was evaluated in the same manner as in Example 1 except that the diazoquinone compound in Example 1 was changed to the formula (Q-3).

[0069]

EXAMPLE 4 In the synthesis of the polyamide in Example 1, 2,2-bis (3-amino-4hydroxyphenyl) hexafluoropropane was reduced to parts by weight (0.475 mol), and instead of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane 6.
2 parts by weight and 5-norbornene-2,3-dicarboxylic anhydride 6 instead of phthalic anhydride as a terminal blocking agent
A polyamide is synthesized using 5.6 parts by weight (0.4 mol),
Otherwise, the photosensitive characteristics were evaluated in the same manner as in Example 1.

[0070]

Example 5 2,2-bis (3-amino-4hydroxyphenyl) hexafluoropropane 2 under a stream of dry nitrogen
93.0 parts by weight (0.8 mol) and 253.1 parts by weight of pyridine (3.2 mol) were dissolved in 2.0 L of acetone, and -15
Cooled to ° C. 370.6 parts by weight (1.76 parts by weight) of trimellitic anhydride chloride dissolved in 500 mL of acetone was added thereto.
Mol) was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After the completion of the dropwise addition, the reaction was carried out at 0 ° C. for 4 hours. After concentrating this solution with an evaporator, it is poured into 5 L of petroleum ether,
An acid anhydride (6FA) was obtained. This acid anhydride (6FA) 3
57.2 parts by weight (0.5 mol), 136.6 parts by weight of 3-hydroxybenzyl alcohol (1.1 mol), NMP12
After mixing 50 mL and 87.0 parts by weight (1.1 mol) of pyridine, the mixture was stirred at room temperature for 16 hours to perform esterification.

Thereafter, 1-hydroxy-1,2,3,-
Benzotriazole (1.1 mol) was added, and a solution prepared by dissolving 227.0 parts by weight (1.1 mol) of dicyclohexylcarbodiimide (DCC) in 230 parts by weight of NMP under ice cooling was added dropwise to obtain a dicarboxylic acid derivative. Next, 4,4′-diaminodiphenyl ether 110.1 was added to the reaction mixture.
A solution prepared by dissolving 0.5 parts by weight of NMP in 350 mL of NMP was added thereto, and the mixture was stirred and reacted at room temperature for 3 hours. Then 5
-Norbornene-2,3-dicarboxylic anhydride 32.8
Part by weight (0.2 mol) was added, and the mixture was further reacted at room temperature for 4 hours. After the reaction solution was filtered to remove insolubles,
The solution was put into a solution of methanol = 10/1, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamide.

A photosensitive resin composition was prepared in the same manner as in Example 1 except that this polymer was used, and the photosensitive characteristics were evaluated.

[0073]

Embodiment 6 <Production of Relief Structure> The silicon wafer having a good pattern shape obtained in the above-mentioned Embodiments 1 to 5 was placed in a vertical curing furnace (manufactured by Koyo Lindberg).
Curing (heating and curing treatment) was performed at 350 ° C. for 2 hours in a nitrogen atmosphere. As a result, a pattern having via holes with a diameter of 5 μm was obtained with good shape in any of the silicon wafers.

[0074]

Comparative Example 1 Photosensitive characteristics were evaluated in the same manner as in Example 1 except that the diazoquinone compound in Example 1 was changed to Formula (Q-4).

[0075]

Comparative Example 2 Photosensitive characteristics were evaluated in the same manner as in Example 1 except that the diazoquinone compound in Example 1 was changed to the formula (Q-5). Table 1 shows the evaluation results of Examples 1 to 5 and Comparative Examples 1 and 2 as described above.

[0076]

[Table 1]

The structures of the diazoquinone compounds (Q1-Q5) and 6FA used in the above Examples and Comparative Examples are as follows.

[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

EFFECT OF THE INVENTION By using the positive photosensitive resin composition of the present invention, a general-purpose 2.38% TMAH developer having high sensitivity and high resolution patterning characteristics in a thick film having a film thickness exceeding 10 μm. An extremely useful material that can maintain a high residual film ratio even if is used is provided. Further, a relief structure having high heat resistance can be obtained by the production method of the present invention.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) H01L 21/027 H01L 21/30 502R

Claims (4)

[Claims] (A) 100 parts by weight of a polyamide having a repeating unit represented by the general formula (1), and (Wherein X 1 is a group having at least 2 carbon atoms)
To a tetravalent organic group, Y1 is a divalent to hexavalent organic group having at least 2 or more carbon atoms, p and q are 0 or an integer of 1 to 4, R1 is hydrogen or a group having 1 to 20 carbon atoms. An organic group, having at least one phenolic hydroxyl group when both p and q are 0, n is an integer from 2 to 1000, m is 0 or an integer from 1 to 2, provided that m, p and q are 0 at the same time There is no. (B) A positive photosensitive resin composition containing 1 to 100 parts by weight of a photosensitive diazoquinone compound represented by the following general formula (2) as an essential component. Embedded image Wherein Z is a tetravalent organic group, R1, R2, R3, and R4 are monovalent organic groups, k is 0 or 1, r, s, t, and u are 0 or 1.
At least one of the integers Q and Q is a group shown below, and the rest are hydrogen atoms. ) 2. The positive photosensitive resin composition according to claim 1, wherein the polyamide has a repeating unit represented by the formula (3). Embedded image (Wherein X2 is a tetravalent aromatic group, Y2 is a divalent aromatic group, n
Is the same as above) 3. The positive photosensitive resin composition according to claim 1, wherein in the photosensitive diazoquinone compound represented by the general formula (2), Z is selected from the group of the following formulas. Embedded image 4. A positive photosensitive resin composition according to claim 1, which is applied to a substrate in the form of a layer or a film, and exposed to actinic light through a mask. A method for producing a high heat-resistant relief structure, comprising directly irradiating an electron beam or an ion beam, eluting or removing an exposed portion or an irradiated portion, and then sintering the obtained relief structure.