JPH1195439A - Production of positive type photosensitive resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin having high sensitivity, giving a pattern with a high rate of a residual film and excellent in adhesion to a sealing resin by blending specified amts. of a specified polyamide, a photosensitive diazoquinone compd. and a specified phenol compd. SOLUTION: A polyamide is obtd. by allowing 1 mol arom. dicarboxylic acid deriv. represented by formula I to react with 0.6-0.99 mol arom. amiophenol compd. represented by formula II and 0.01-0.4 mol diaminosiloxane represented by formula III in a polar solvent at 10-100 deg.C and 100 pts.wt. of the polyamide is blended with 1-100 pts.wt. photosensitive diazoquinone compd. and 1-50 pts.wt. phenol compd. represented by formula IV to produce the objective positive type photosensitive resin. Since the arom. carboxylic acid deriv. reacts readily with a compd. having an amino group to form an amide compd., the resultant polyamide has a high mol.wt. favorable to the photosensitive resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a positive photosensitive resin which can obtain a pattern having high sensitivity and a high residual film ratio and which has excellent adhesion to a sealing resin.

[0002]

2. Description of the Related Art Conventionally, a polyimide resin having excellent heat resistance and excellent electrical and mechanical properties has been used for a surface protective film and an interlayer insulating film of a semiconductor element. There is a demand for remarkable improvement in heat cycle resistance and heat shock resistance due to high integration, large size, thinner and smaller sealing resin package, and shift to surface mounting by solder reflow. Is becoming necessary. On the other hand, as a photosensitive polyimide resin, a technique for imparting photosensitivity to the polyimide resin itself has recently attracted attention, there is formula (VI) and the like.

[0003]

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When this is used, a part of the pattern forming process can be simplified, which has the effect of shortening the process.
Since a solvent such as methyl-2-pyrrolidone is required, there is a problem in safety and pollution. Therefore, recently, a positive photosensitive resin capable of developing with an aqueous alkali solution has been developed. For example, Japanese Patent Publication No. 1-46862 discloses a positive photosensitive resin composed of a polybenzoxazole resin and a diazoquinone compound. It has high heat resistance, excellent electrical properties, and fine workability, and has the potential as a resin for interlayer insulation as well as for wafer coating. The mechanism of development of this positive photosensitive resin is that the diazoquinone compound in the unexposed area is insoluble in the alkaline aqueous solution, but the exposure causes the diazoquinone to undergo chemical modification and become soluble in the alkaline aqueous solution. By utilizing the difference in solubility between the exposed part and the unexposed part, a coating film pattern can be formed only in the unexposed part.

When these photosensitive resins are actually used,
Particularly problematic is the sensitivity of the photosensitive resin. If the sensitivity is low, the exposure time per wafer becomes long, and the throughput decreases. In order to improve the sensitivity of the photosensitive resin, for example, if the molecular weight of the polybenzoxazole resin as the base resin is reduced, a problem occurs that the film loss at the time of development of the non-exposed portion becomes large and the pattern shape becomes poor. In addition, the adhesiveness between the photosensitive resin and the sealing resin is poor, peeling occurs at the interface, there is a problem in practicality, and a photosensitive resin having more excellent adhesion with the sealing resin is strongly demanded. Has become.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a positive photosensitive resin which is excellent in adhesion to a sealing resin and which can provide a pattern having a high sensitivity and a high residual film ratio. And

[0007]

The present invention provides a compound represented by the general formula (I):
(A) 0.6 to 0.99 mol of the aromatic aminophenol compound (B) represented by the general formula (II) per 1 mol of the aromatic dicarboxylic acid derivative (A) represented by the following formula, and diamino represented by the general formula (III) The photosensitive diazoquinone compound (E) is added in an amount of 1 to 100 parts by weight to 100 parts by weight of the polyamide (D) obtained by reacting 0.01 to 0.4 mol of the siloxane (C) with a polar solvent at a temperature of 10 to 100 ° C. And a phenol compound (F) represented by the formula (IV): 1 to 50 parts by weight.

[0008]

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[0009]

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[0010]

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[0011]

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[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The aromatic dicarboxylic acid derivative of the general formula (I) easily reacts with a compound having an amino group to form an amide compound. Therefore, a high-molecular-weight polyamide can be produced by reacting with a bifunctional amino compound, which is preferable. As a reaction condition for producing a polyamide, a temperature of 10 to 100 ° C. during polar dissolution is preferable. Aromatic dicarboxylic acid derivatives and bifunctional amino compounds are preferred because they are easily dissolved in highly polar solvents and the reaction proceeds uniformly. When the reaction temperature is lower than 10 ° C., the progress of the reaction becomes extremely slow and productivity is deteriorated. On the other hand, when the temperature is higher than 100 ° C., side reactions increase and it becomes difficult to obtain a polyamide having a high molecular weight.

A method of directly synthesizing a dicarboxylic acid dichloride compound with a diamine compound by a method of synthesizing a polyamide has been conventionally used. However, in this method, hydrochloric acid is generated during the reaction, so that a hydrochloric acid trapping agent such as triethylamine is used. It is common to coexist. However, the polyamide obtained in this way contains chloride ions in the order of several percent in the resin, so it is not suitable in terms of reliability when applied to electronic materials. Purification for removal had to be performed. On the other hand, according to the production method of the present invention, there is no such contamination of chlorine ions, and it can be used as a highly reliable electronic material.

The aromatic dicarboxylic acid derivative of the present invention is not particularly limited. For example, 1 mol of the corresponding aromatic dicarboxylic acid and 2 mol of hydroxybenzotriazole are dissolved in N-methyl-2-pyrrolidone. It can be easily synthesized by allowing a dehydrating condensing agent such as dicyclohexylcarbodiimide to react dropwise at a low temperature of 5 ° C. or lower. X of the aminophenol of the general formula (II) used in the present invention is, for example,

[0015]

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However, the present invention is not limited to these. Among them, the most sensitive one is

[0017]

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[0018] It is more selected. Y in the formula (I) is, for example,

[0019]

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However, the present invention is not limited to these. Among these, the most sensitive

[0021]

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Further, the diaminosiloxane of the formula (III) is, for example,

[0023]

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However, the present invention is not limited to these. Diaminosiloxane is used, for example, when adhesion is particularly required to a substrate such as a silicon wafer. The use ratio b can be up to 40.0 mol%. If it exceeds 40.0 mol%, the solubility of the resin is reduced, and even when the pattern processing method of the present invention is used, scum is generated and pattern processing cannot be performed.

If the amount is less than 0.1 mol%, the effect of improving adhesion cannot be obtained, so that it is not preferable. When using X and Y, one type or a mixture of two or more types may be used. The diazoquinone (E) used in the present invention is a compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure, and is described in U.S. Pat. Nos. 2,772,972 and 2,7.
No. 97,213, and No. 3,669,658. For example,

[0026]

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[0027]

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Among these, those which are particularly preferable from the viewpoint of a high residual film ratio are as follows.

[0029]

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## EQU1 ## The amount of the photosensitive diazidoquinone compound (E) to be mixed with the polyamide (D) is polyamide 1
If the amount is from 1 to 100 parts by weight, and if the amount is less than 1 part by weight, the patterning property of the resin is poor, and if it exceeds 100 parts by weight, the tensile elongation of the film is significantly reduced.

A dihydropyridine derivative can be added to the positive photosensitive resin composition of the present invention, if necessary, to enhance the photosensitive characteristics. Examples of the dihydroxypyridine derivative include 2,6-dimethyl-3,5-diacetyl-4- (2'-nitrophenyl) -1,4-dihydropyridine and 4- (2'-nitrophenyl) -2,6-dimethyl-3 , 5-Dicarboethoxy-1,4-dihydropyridine, 4- (2 ', 4'-dinitrophenyl)-
2,6-dimethyl-3,5-carbomethoxy-1,4-
Dihydropyridine and the like can be mentioned. In the method for producing a positive photosensitive resin of the present invention, the general formula (I
It is important to include the phenol compound represented by V).

[0032]

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The technique of adding a phenol compound to a positive resist composition is disclosed in, for example, JP-A-3-20.
0251, JP-A-3-200252, JP-A-3-200
253, JP-A-3-200254, JP-A-4-165
0, JP-A-4-1651, JP-A-4-11260, JP-A-4-12356, JP-A-4-12357, JP-A-7-
159990. However, phenol compounds such as those described above have a small effect of improving sensitivity even when used in a positive photosensitive resin containing a polyamide as a base resin in the present invention. However, when the phenol compound represented by the general formula (IV) in the present invention is used, the dissolution rate in the exposed area increases, and the sensitivity improves. Also,
The film loss in the unexposed portion as seen when the sensitivity is increased by lowering the molecular weight is also very small.

Further, in the present invention, it has been found that the addition of the phenol compound represented by the general formula (IV) can provide a positive photosensitive resin having improved adhesion to the sealing resin as a new property. As the compound represented by the general formula (IV),

[0035]

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[0036]

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[0037]

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Examples are, but not limited to, these. Among these, particularly preferred in terms of sensitivity and residual film ratio,

[0039]

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The compound represented by the general formula (V) or (VI) alone or in the form of a mixture contains 50% or more of the whole phenol compound (F). Phenol compound (F)
Is preferably 1 to 50 parts by weight with respect to the polyamide (A). If the amount is less than 1 part by weight, the effect of improving sensitivity cannot be obtained, and if the amount is more than 50 parts by weight, the remaining film portion is greatly reduced, which is not practical. Additives such as a leveling agent and a silane coupling agent can be added to the positive photosensitive resin in the present invention, if necessary.

In the present invention, these components are dissolved in a solvent and used in the form of a varnish. Examples of the solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-
Dimethylacetamide, dimethylsulfoxide, 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 may be used alone or in combination.

In the method of using the photosensitive resin of the present invention, first, the composition is applied to a suitable support, for example, a silicon wafer, ceramic, or aluminum substrate. The coating method includes spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like. Next, after pre-baking at 60 to 120 ° 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, but 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. As the developer, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as 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 An aqueous solution of an alkali such as a quaternary ammonium salt and an aqueous solution obtained by adding a suitable amount of a water-soluble organic solvent such as an alcohol such as methanol or ethanol or a surfactant thereto can be suitably used. As a developing method, a system such as spray, paddle, immersion, and 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 high heat resistance is obtained. The photosensitive resin composition according to the present invention is useful not only for semiconductor applications, but also as interlayer insulation for multilayer circuits, cover coats for flexible copper clad boards, solder resist films, liquid crystal alignment films, and the like. Hereinafter, the present invention will be described specifically with reference to examples.

[0043]

【Example】

Example 1 Synthesis of Polyamide 492.45 g (1 mol) of an aromatic dicarboxylic acid derivative obtained by reacting 1 mol of diphenyl ether-4,4'-dicarboxylic acid with 2 mol of hydroxybenzotriazole and 2,2-bis ( 351.61 g of 3-amino-4-hydroxyphenyl) hexafluoropropane (0.9
6 mol), 1,3-bis (3-aminopropyl) -1,
9.94 g of 1,3,3-tetramethyldisiloxane
(0.04) was placed in a 5 l four-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, and 2,000 g of N-methyl-2-pyrrolidone was added to dissolve it. Was. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath to obtain polyamide D-1.

Preparation of photosensitive resin composition 100 parts by weight of synthesized polyamide (D-1), 25 parts by weight of diazoquinone (B) having the following structure

[0045]

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A phenol compound (F) having the following structure
15 parts by weight

[0047]

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[0048] N-methyl-2-pyrrolidone (hereinafter referred to as N
After dissolving in 200 parts by weight of MP, the mixture was filtered through a 0.2 μm Teflon filter to obtain a photosensitive resin composition.

Characteristic evaluation After applying this photosensitive varnish on a silicon wafer by using a spray coater, the photosensitive varnish was applied to a hot plate at 120 ° C.
For 2 minutes to obtain a coating film having a thickness of about 5 μm. The coating film is passed through a reticle by a g-line stepper exposure machine NSR-1505G3A (manufactured by Nikon) to make the coating from 50 mJ / cm ² to 20 mJ / cm ^2.
mJ / cm ² increase at a time and was exposed to 540mJ / cm ^2. Next, the exposed portion was dissolved and removed by immersion in a 0.79% tetramethylammonium hydroxide aqueous solution for 30 seconds, and then rinsed with pure water for 30 seconds. As a result, it was confirmed that a pattern was formed from a portion irradiated with an exposure amount of 200 mJ / cm ² . (The sensitivity is 2
00 mJ / cm ² ). The remaining film ratio at this time (film thickness after development /
The film thickness before development) was as high as 94.3%.

Separately, a photosensitive varnish is similarly coated on a silicon wafer, prebaked, and then placed in an oven.
0 minutes / 150 ° C, 30 minutes / 250 ° C, 30 minutes / 350 ° C
In this order to cure the resin. Furthermore, an epoxy resin composition for semiconductor encapsulation (manufactured by Sumitomo Bakelite Co., Ltd., EME-6300H) is placed on the cured film at 2 mm × 2 mm × 2.
mm (width x length x height). The sealing epoxy resin composition formed on the cured polybenzoxazole resin film was peeled off using Tensilon, and the shear strength was measured. The result was 4.2 kg / mm ² .

[Evaluation of Reliability of Semiconductor Device] Using a simulated element wafer having an Al circuit on the surface, the above photosensitive resin was applied to a final thickness of 5 μm, and then subjected to pattern processing and finally baked. After that, it is divided by chip size into 16
pinDIP (Dual Inline Package)
e) is mounted on a lead frame using a conductive paste and then molded with an epoxy resin for semiconductor encapsulation (manufactured by Sumitomo Bakelite Co., Ltd., EME-6300H) to form a 16p.
inDIP was obtained. 85 ° C / 85
% Humidity for 168 hours, immersed in a solder bath at 260 ° C. for 10 seconds, and then subjected to high-temperature, high-humidity pressure cooker treatment (125 ° C., 2.3 atrm, 100% RH).
To check for open defects in the Al circuit. Table 1 shows the results.

Example 2 Evaluation was performed by changing the phenol compound (F) in Example 1 to P-2. Example 3 Evaluation was performed by changing the phenol compound (F) in Example 1 to P-3. Example 4 The amount of the phenol compound (F) added in Example 1 was changed to 5
The evaluation was performed in parts by weight.

Example 5 A polyamide was synthesized using an isophthalic acid ester derivative obtained by reacting isophthalic acid with hydroxybenzotriazole instead of the diphenyl ether 4,4'-dicarboxylic acid derivative used in the synthesis of the polyamide in Example 1. Then, the same evaluation as in Example 1 was performed. Example 6 In the synthesis of the polyamide in Example 1, 3,3'-diamino-4,4 'was used instead of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
A polyamide was synthesized using 0.96 mol of dihydroxydiphenylsulfone, and the same evaluation as in Example 1 was performed. Example 7 In Example 1, the photosensitive diazoquinone compound was replaced with Q-2.
The same procedure was performed except that the above was replaced. Example 8 In the synthesis of polyamide in Example 1, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was reduced to 323.63 g (0.90 mol), and 1,3-bis (3- Aminopropyl) -1,1,
24.85 g of 3,3-tetramethyldisiloxane (0.
The procedure was the same except that the amount was increased to 10 mol).

Comparative Example 1 A polyamide was synthesized by using 1 mol of diphenyl ether 4,4'-dicarboxylic acid chloride in place of the compound synthesized from diphenyl ether 4,4'-dicarboxylic acid and hydroxybenzotriazole in Example 1 to obtain chlorine. The same evaluation as in Example 1 was performed without performing any purification for removing ions. Comparative Example 2 Evaluation was performed in Example 1 without adding a phenol compound. Comparative Example 3 Evaluation was made in Example 5 without adding a phenol compound. Comparative Example 4 Evaluation was made in Example 6 without adding a phenol compound. Comparative Example 5 The amount of the phenol compound added in Example 1 was 0.5
The evaluation was performed by reducing the weight to parts by weight. Comparative Example 6 The evaluation was performed by increasing the amount of the phenol compound added in Example 1 to 60 parts by weight. Comparative Example 7 The evaluation was performed by replacing the phenol compound in Example 1 with P-4. Comparative Example 8 The evaluation was performed by replacing the phenol compound in Example 1 with P-5. Comparative Example 9 The evaluation was performed by replacing the phenol compound in Example 1 with P-6.

[0055]

[Table 1]

[0056]

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[0057]

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[0058]

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[0059]

According to the present invention, a pattern of a high sensitivity and a high residual film ratio can be obtained, and a positive photosensitive resin composition having excellent adhesion to a sealing resin can be obtained.

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI H01L 21/027 H01L 21/30 502R (72) Inventor Naoshi Takeda 2-5-8 Higashishinagawa, Shinagawa-ku, Tokyo Sumitomo Bakelite Co., Ltd. In company

Claims (6)

[Claims] 1. An aromatic aminophenol compound (B) 0.6 to 0.9 represented by the general formula (II) per mole of the aromatic dicarboxylic acid derivative (A) represented by the general formula (I).
9 mol, 0.01 to 0.4 mol of diaminosiloxane (C) represented by the general formula (III) in a polar solvent is added to 10 to 1
Polyamide (D) 1 obtained by reacting at a temperature of 00 ° C.
To 100 parts by weight of the photosensitive diazoquinone compound (E)
A method for producing a positive photosensitive resin, which comprises mixing 0 parts by weight with 1 to 50 parts by weight of a phenol compound (F) represented by the general formula (IV). Embedded image Embedded image Embedded image Embedded image 2. The phenolic compound (F) has the general formula (V)
Or (VI). The method for producing a positive photosensitive resin according to claim 1, wherein the method is represented by (VI). Embedded image 3. The positive type according to claim 1, wherein the compound represented by the general formula (V) or (VI) contains 50% or more of the whole phenolic compound (F) alone or in the form of a mixture. A method for producing a photosensitive resin. 4. X in the aminophenol compound of the general formula (II) is 4. The method for producing a positive photosensitive resin according to claim 1, wherein the positive photosensitive resin is selected from the group consisting of: 5. An aromatic dicarboxylic acid derivative represented by the general formula (I) wherein Y is 5. The method for producing a positive photosensitive resin according to claim 1, wherein the positive photosensitive resin is selected from the group consisting of: 6. The photosensitive diazoquinone (E) is represented by the following formula: The method of claim 1, 2, 3, 4, or
6. The method for producing a positive photosensitive resin according to 5.