JP3207352B2 - Positive photosensitive resin composition - Google Patents

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 capable of obtaining a pattern having a high sensitivity and a high residual film ratio and having 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 integration, enlargement, thinning and miniaturization of the sealing resin package, transition to surface mounting by solder reflow, etc. It is becoming needed. On the other hand, a technique for imparting photosensitivity to the polyimide resin itself has recently attracted attention. For example, the following formula (VI) is given as a photosensitive polyimide resin.

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When this is used, a part of the pattern forming process can be simplified and the process can be shortened.
Since a solvent such as methyl-2-pyrrolidone is required, there is a problem in safety and handling. Therefore, recently, a positive photosensitive resin that can be developed with an alkaline aqueous 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, fine workability,
It 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 such that the unexposed portion of the diazoquinone compound is insoluble in the alkaline aqueous solution, and the exposure causes the diazoquinone compound to undergo a chemical change and become soluble in the alkaline aqueous solution. Utilizing the difference in solubility between the exposed part and the unexposed part,
This makes it possible to create a coating film pattern of only the unexposed portions. When these photosensitive resins are actually used, a particular problem is the sensitivity of the photosensitive resin. If the sensitivity is low, the exposure time per wafer becomes long, and the throughput decreases. So, to improve the sensitivity of the photosensitive resin,
For example, when the molecular weight of the polybenzoxazole resin as the base resin is reduced, the film loss at the time of development of the non-exposed portion becomes large, causing a problem that the pattern shape is deteriorated.
In addition, the adhesion 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 with more excellent adhesion to the sealing resin is strongly demanded. Has become.

[0004]

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

[0005]

The present invention provides a compound represented by the general formula (I):
And 100 to 100 parts by weight of a photosensitive diazoquinone compound (B) represented by the formula (II):
A positive-type photosensitive resin composition comprising 1 to 50 parts by weight of a phenol compound (C) represented by the formula:

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[0006]

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The polyamide of the formula (I) comprises bisaminophenol having the structure of X and dicarboxylic acid having the structure of Y. When the polyamide is heated at about 300 to 400 ° C., the ring is closed, and the heat resistance of polybenzoxazole is obtained. Changes to resin. X of the polyamide (1) of the present invention is, for example,

Embedded image Etc., but are not limited to these.

[0008] Among them, those having particularly high sensitivity include:

Embedded image It is more chosen.

Further, Y in the formula (I) is, for example,

Embedded image Etc., but are not limited to these.

[0010] Among these, those with particularly high sensitivity

Embedded image It is more chosen.

Further, Z in the formula (1) is, for example,

Embedded image Etc., but are not limited to these.

Z in the formula (1) is used, for example, when adhesion is particularly required to a substrate such as a silicon wafer.
Can be used up to. If it exceeds 40.0 mol%, the solubility of the resin is extremely reduced, scum is generated, and pattern processing cannot be performed. When using X, Y, and Z, one type or a mixture of two or more types may be used.

The photosensitive diazoquinone compound used in the present invention is a compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure, and is disclosed in US Pat. Nos. 2,772,972 and 2,797, 21
No. 3,669,658. For example, the following are mentioned.

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[0014]

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Among them, the followings are particularly preferable from the viewpoint of a high residual film ratio.

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The compounding amount of the photosensitive diazidoquinone compound (B) to the polyamide (A) is 1 to 100 parts by weight with respect to 100 parts by weight of the polyamide. If the compounding amount is less than 1 part by weight, the patterning property of the resin is poor. Conversely, if it exceeds 100 parts by weight, the tensile elongation of the film is significantly reduced.

A dihydroxypyridine 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-dicarbethoxy-1,4-dihydropyridine, 4- (2 ', 4'-dinitrophenyl)
-2,6-dimethyl-3,5-carbomethoxy-1,4
-Dihydropyridine and the like.

It is important that the positive photosensitive resin composition of the present invention further contains a phenol compound represented by the general formula (II).

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Techniques for adding a phenolic compound to a positive resist composition include, for example, those disclosed in JP-A-3-2002.
No. 51, JP-A-3-200252, JP-A-3-20052
JP-A-200253, JP-A-3-200254, JP-A-4-1650, JP-A-4-1651, JP-A-4-11260, JP-A-4-123
No. 56, JP-A-4-12357. 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 (II) in the present invention is used, the dissolution rate in the exposed area increases, and the sensitivity improves. Further, the film loss in the unexposed portion as seen when the sensitivity is increased by reducing the molecular weight is very small. Further, in the present invention, as a new property by adding the phenol compound represented by the general formula (II), it has been found that a positive photosensitive resin composition having improved adhesion to a sealing resin can be obtained. Was.

The compounds represented by the general formula (II) include, but are not limited to, the following.

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[0021]

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[0022]

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[0023]

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Among these, particularly preferred in terms of sensitivity and residual film ratio are:

Embedded image The compound represented by the general formula (IV) or (V) is contained alone or in the form of a mixture in an amount of 50% by weight or more in the total phenol compound (C). The amount of the phenol compound (C) to be added is preferably 1 to 50 parts by weight based on 100 parts by weight of 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 50
If the amount is more than 10 parts by weight, the residual film ratio is greatly reduced, or precipitation occurs during frozen storage, which is not practical.

If necessary, additives such as a leveling agent and a silane coupling agent can be added to the positive photosensitive resin composition of the present invention. 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, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and 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 positive photosensitive resin composition of the present invention, the composition is first applied to a suitable support, for example, a silicon wafer, ceramic, aluminum substrate or the like. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, and roll coating. 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. Examples of the developer 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, diethylamine, and di-n. Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, and quaternary ammoniums such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. An aqueous solution of an alkali such as a salt or 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 positive 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.

[0027]

The present invention will be described below in detail with reference to examples. << Example 1 >> * Synthesis of polyamide 2,2-bis (3-amino-4-hydroxyphenyl)
36.6 parts (0.100 mol) of hexafluoropropane were dissolved in 150 parts by weight of N, N-dimethylacetamide and 33.2 (0.420 mol) of pyridine. Next, 17.0 parts by weight (0.084 mol) of terephthalic acid chloride and 4.3 parts by weight (0.021 mol) of isophthalic acid chloride dissolved in 100 parts by weight of cyclohexanone were used.
Was added dropwise at -10 to -15 ° C over 30 minutes, followed by stirring at room temperature for 4 hours to complete the reaction. After the reaction mixture is filtered, the solution is poured into water and represented by the desired general formula (I):
X is a mixture of the following formulas X-1 and Y is a mixture of the following formulas Y-1 and Y-2 to precipitate a polyamide (A ₁ ) consisting of a = 100 and b = 0. The precipitate was collected by filtration, washed sufficiently with water, and then dried at 80 ° C. under vacuum overnight.

Preparation of Positive-Type Photosensitive Resin Composition 100 parts by weight of synthesized polyamide (A ₁ ), 25 parts by weight of diazoquinone (Q1) having a structure of the following formula, and a phenol compound (P-1) having a structure of the following formula ) 15 parts by weight were dissolved in 200 parts by weight of N-methyl-2-pyrrolidone and then filtered through a 0.2 μm Teflon filter to obtain a photosensitive resin composition.

* Characteristic evaluation After coating this positive photosensitive resin composition on a silicon wafer by using a spin coater, it was dried in an oven at 70 ° C. for 1 hour to obtain a coating film having a thickness of about 3 μm. A g-line stepper exposure machine NSR-1505G3A (Nikon
The exposure from 50 mJ / cm ² through a reticle to 20 mJ / cm ² increments increased by 540mJ / cm ² was performed by Co.). 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 200 mJ / cm ² ). At this time, the residual film ratio (film thickness after development / film thickness before development) was as high as 91.3%. Separately, a positive photosensitive resin composition 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 (Sumitomo Bakelite Co., Ltd.)
Manufactured by EME-6300H) 2 x 2 x 2 mm (horizontal x vertical 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. As a result, it was 3.2 kg / mm ² .

Example 2 Evaluation was made by changing the phenolic compound in Example 1 to the following formula P-2. << Example 3 >> The evaluation was performed by replacing the phenol compound in Example 1 with the following formula P-3. << Example 4 >> The phenolic compound (P-
Evaluation was performed by adding 5 parts by weight of 1). Example 5 In the synthesis of polyamide in Example 1, diphenyl ether-4,4'-dicarboxylic acid chloride was used instead of terephthalic acid chloride and isophthalic acid chloride, and the compound was represented by the general formula (I), and X was the following formula X-
1, a polyamide (A ₂ ) having Y = the following formula Y = a = 100 and b = 0 was synthesized, and the other evaluations were performed in the same manner as in Example 1.

Example 6 In the synthesis of the polyamide in Example 1, diphenyl ether-4,4'- was used instead of terephthalic acid chloride and isophthalic acid chloride.
Dicarboxylic acid chloride is used and 2,2-bis (3
-Amino-4-hydroxyphenyl) hexafluoropropane, instead of 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, is represented by the general formula (I)
X is the following formula X-2, Y is the following formula Y-3,
= 100, and the synthesis of b = 0 a polyamide (A _3), others were evaluated in the same manner as in Example 1. Example 7 In the synthesis of the polyamide in Example 1, diphenyl ether-4,4'-dicarboxylic acid chloride was used instead of terephthalic acid chloride and isophthalic acid chloride, and 2,2-bis (3-amino-4 -Hydroxyphenyl) Instead of hexafluoropropane, 3,3'-diamino-4,4'-dihydroxydiphenyl ether is used, represented by the general formula (I), wherein X is the following formula X-3, and Y is the following formula In Y-3, a = 100, b =
Synthesis of a polyamide (A ₄ ) consisting of No. 0 was carried out, and a diazoquinone (Q2) having the following structure was used as the diazoquinone to obtain a photosensitive resin composition. Other evaluations were conducted in the same manner as in Example 1. << Example 8 >> In the synthesis of the polyamide in Example 1, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added with 34.8 parts by weight (0.08 parts by weight).
95 mol), and 1.24 parts by weight (0.005 mol) of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane was added instead. X is the following formula X-1, and Y is the following formula Y-1
And Y-2, Z is the following formula Z-1, a = 95, b
= A five polyamide (A ₅₎ were synthesized, others were evaluated in the same manner as in Example 1.

Comparative Example 1 Evaluation was made in Example 1 without adding a phenol compound. << Comparative Example 2 >> Evaluation was made in Example 5 without adding a phenol compound. << Comparative Example 3 >> Evaluation was made in Example 6 without adding a phenol compound. << Comparative Example 4 >> The evaluation was performed by reducing the amount of the phenol compound added in Example 1 to 0.5 part by weight. << Comparative Example 5 >> The evaluation was performed by increasing the amount of the phenol compound added in Example 1 to 60 parts by weight. << Comparative Example 6 >> The phenol compound in Example 1 was replaced with P-
The evaluation was performed in place of 4. << Comparative Example 7 >> The phenol compound in Example 1 was replaced with P-
The evaluation was performed in place of 5. << Comparative Example 8 >> The phenol compound in Example 1 was changed to P-
The evaluation was performed in place of 6. The evaluation results of Examples 1 to 8 and Comparative Examples 1 to 8 are shown in Table 1.

[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

[Table 1]

[0039]

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 (56) References JP-A-64-6947 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 77/00-77/12 G03F ⁷ /00-7 / 18 CAS

Claims (6)

(57) [Claims] 1. 100 parts by weight of a polyamide (A) represented by the general formula (I) and a photosensitive diazoquinone compound (B)
A positive photosensitive resin composition comprising 1 to 100 parts by weight and 1 to 50 parts by weight of a phenol compound (C) represented by the general formula (II). Embedded image Embedded image 2. The phenol compound (C) is represented by the general formula (II)
The positive photosensitive resin composition according to claim 1, which is a phenol compound represented by I). Embedded image 3. The positive phenol compound according to claim 2, wherein the phenol compound is a compound represented by the general formula (IV) or (V), and contains 50% by weight or more of the phenol compound (C) alone or in a mixture. -Type photosensitive resin composition. Embedded image 4. X in the polyamide of the general formula (I)
Is selected from the following: The positive photosensitive resin composition according to claim 1, 2 or 3. Embedded image 5. Y in the polyamide of the general formula (I)
Is selected from the following: The positive photosensitive resin composition according to claim 1, 2, 3, or 4. Embedded image 6. The positive photosensitive resin composition according to claim 1, wherein the photosensitive diazoquinone compound (B) is selected from the following. Embedded image