JPH1165107A - Positive type photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin compsn. excellent in adhesion to a sealing resin by using specified amts. of a specified polyamide, a photosensitive diazoquinone compd. and a specified phenol compd. SOLUTION: The photosensitive resin compsn. consists of 100 pts.wt. polyamide represented by formula I, 1-100 pts.wt. photosensitive diazoquinone compd. and 1-30 pts.wt. phenol compd. represented by formula II. In the formula I, X is a tetravalent arom. group, Y is a divalent arom. group, Z is -R1 -Si(R3 ) (R4 )-O-Si(R3 ) (R4 )-R2 -, R1 and R2 are each divalent org. group, R3 and R4 are each monovalent org. group, (a) and (b) show molar fraction, a+b = 100 mol.%, (a) is 60.0-100.0 mol.%, (b) is 0-40.0 mol.% and (n) is 2-500. In the formula II, R5 is H or alkyl and R6 -R11 are individually H, halogen, hydroxyl, alkyl, alkoxy or cycloalkyl.

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 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 (3) is given as a photosensitive polyimide resin.

[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 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 precursor and a diazoquinone compound.
It has high heat resistance, excellent electrical properties and fine workability, and has the potential not only as a wafer coat but also as an interlayer insulating resin. 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. 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.

[0005] When these photosensitive resins are used for an actual semiconductor for wafer coating, peeling occurs at the interface between the wafer coating resin and the sealing resin, often causing a problem of lowering the reliability of the semiconductor. . The reason for this is that the adhesion between the wafer coat resin and the sealing resin is low, and a photosensitive resin having more excellent adhesion with the sealing resin has been required.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a positive photosensitive resin having excellent adhesion to a sealing resin.

[0007]

According to the present invention, there is provided a compound represented by the general formula (1):
And 100 to 100 parts by weight of a photosensitive diazoquinone compound (B) represented by the formula (2):
A positive-type photosensitive resin composition comprising 1 to 30 parts by weight of a phenol compound (C) represented by the formula:

[0008]

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[0009]

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(Wherein, R ₅ represents a hydrogen atom or an alkyl group, and R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ each represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group,
Shows one selected from an alkoxy group and a cycloalkyl group)

The polyamide of the formula (1) is composed of bisaminophenol having the structure of X and dicarboxylic acid having the structure of Y. When this 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,

[0012]

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However, the present invention is not limited to these. Among them, particularly preferred are:

[0014]

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[0015] It is more selected. Also, Y of the formula (1)
Is, for example,

[0016]

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However, the present invention is not limited to these. Particularly preferred among these are:

[0018]

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It is more selected. Further, equation (1)
Z is, for example,

[0020]

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However, the present invention is 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.
About the use ratio b, it can be used up to 40.0 mol%. 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 described in US Pat. Nos. 2,772,972 and 2,797,213.
No. 3,669,658.
For example, the following are mentioned.

[0023]

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[0024]

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Among these, the following are particularly preferred.

[0026]

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The compounding amount of the photosensitive diazidoquinone compound (B) to the polyamide (A) is 1 to 100 parts by weight based on 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. On the other hand, 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 dihydropyridine derivative include 2,6-dimethyl-3,5-diacetyl-
4- (2'-nitrophenyl) -1,4-dihydropyridine, 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 (2).

[0030]

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(Wherein, R ₅ represents a hydrogen atom or an alkyl group, and R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ each represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group,
(Indicates one selected from an alkoxy group and a cycloalkyl group.) The phenol compound represented by the general formula (2) is
-46862, it has been found that when added to a positive-type photosensitive resin composed of a polybenzoxazole precursor and a diazoquinone compound, the action mechanism is unknown, but the adhesion to the sealing resin is improved. . Examples of the phenol compound used in the present invention include, but are not limited to, the following.

[0032]

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[0033]

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[0034]

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The addition amount of the phenol compound (C) is preferably 0.1 to 30 parts by weight based on 100 parts by weight of the polyamide (A). If the addition amount is less than 0.1 part by weight, the effect of improving the adhesion cannot be obtained, or if the addition amount exceeds 30 parts by weight, the film loss during development becomes large and the practicality is lacking.

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, alcohol amines 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, buddle, 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 high heat resistance is obtained.

The positive photosensitive resin composition according to the present invention comprises:
It is useful not only for semiconductors but also for interlayer insulation of multilayer circuits, cover coats of flexible copper clad boards, solder resist films, liquid crystal alignment films, and the like.

[0039]

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 the target is represented by the general formula (1):
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 (A1) having 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 photosensitive resin composition 100 parts by weight of synthesized polyamide (A1), 20 parts by weight of diazoquinone (Q1) having the structure of the following formula, and phenol compound (P-1) having the structure of the following formula 5 parts by weight to N
-Methyl-2-pyrrolidone after dissolving in 300 parts by weight,
The mixture was 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 using a spin coater,
After drying at 20 ° C. for 4 minutes, a coating film having a thickness of about 7 μm was obtained. G-line stepper exposure machine NSR-1505G3A
(Manufactured by Nikon Corporation) through a reticle, 50 mJ /
Increase from cm ² 20mJ / cm ² at a time 540mJ /
Exposure was performed up to cm ² . Next, the exposed portion was dissolved and removed by immersing it in a 1.40% aqueous solution of tetramethylammonium hydroxide for 80 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 83.6%.

Separately, a positive photosensitive resin composition was similarly coated on a silicon wafer and prebaked, and then placed in an oven for 30 minutes / 150 ° C., 30 minutes / 250 ° C., 30 minutes /
The resin was heated in the order of 350 ° C. to cure the resin. Further, an epoxy resin composition for semiconductor encapsulation (manufactured by Sumitomo Bakelite Co., Ltd., EME-6300H) is placed on the cured film at 2 × 2 × 2 mm.
It was formed into a size of (width x height 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 3.6 kg / mm ² .

<Example 2> The phenol compound in Example 1 was evaluated in place of the following formula P-2. <Example 3> Evaluation was performed by changing the phenol compound in Example 1 to the following formula P-3. <Example 4> Evaluation was performed by changing the phenol compound in Example 1 to the following formula P-4. <Example 5> The evaluation was performed by changing the phenol compound in Example 1 to the following formula P-5. <Example 6> Evaluation was made by increasing the amount of the phenol compound added in Example 1 to 10 parts by weight.

<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. The following formulas X-1 and Y are the following formulas Y-3, a = 100, b =
A polyamide (A2) consisting of 0 was synthesized, and the other components were evaluated in the same manner as in Example 1.

Example 8 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 acid chloride) was used. -4-Hydroxyphenyl) hexafluoropropane is replaced by 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, represented by the following general formula (1), and X represents the following formulas X-2 and Y Is the following formula Y-3, and a = 1
A polyamide (A3) consisting of 00 and b = 0 is synthesized,
Otherwise, the same evaluation as in Example 1 was performed.

Example 9 In the synthesis of polyamide in Example 1, diphenyl ether 4,4'-dicarboxylic acid chloride was used in place of terephthalic acid chloride and isophthalic acid chloride, and 2,2-bis (3-amino- Instead of 4-hydroxyphenyl) hexafluoropropane, 3,3′-diamino-4,4′-dihydroxydiphenyl ether is used and represented by the general formula (1), wherein X is the following formula X-3, and Y is the following In the formula Y-3, a = 10
A polyamide (A4) consisting of 0 and b = 0 was synthesized, and a diazoquinone (Q
2) was used to obtain a photosensitive resin composition, and the other evaluations were performed in the same manner as in Example 1.

Example 10 In the synthesis of the polyamide in Example 1, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was reduced to 34.8 parts by weight (0.095 mol) instead. 1,3-
1.24 parts by weight of bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane (0.005 mol)
And X is represented by the following formula X-1 and Y
Is a mixture of the following formulas Y-1 and Y-2, and Z is the following formula Z-1
Then, a polyamide (A5) consisting of a = 95 and b = 5 was synthesized, and the other evaluations were the same as in Example 1.

<Comparative Example 1> Evaluation was made without adding the phenol compound in Example 1. <Comparative Example 2> Evaluation was made without adding the phenol compound in Example 7. <Comparative Example 3> Evaluation was made without adding the phenol compound in Example 8. <Comparative Example 4> Evaluation was made by reducing the amount of the phenol compound added in Example 1 to 0.05 parts by weight. Comparative Example 5 Evaluation was made by increasing the amount of the phenol compound added in Example 1 to 40 parts by weight. Example 1
8, Table 1 shows the evaluation results of Comparative Examples 1 to 5.

[0049]

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[0050]

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[0051]

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[0052]

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[0053]

[Table 1]

[0054]

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.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/038 504 G03F 7/038 504 7/075 521 7/075 521 (72) Inventor Naoshi Takeda Higashishinagawa, Shinagawa-ku, Tokyo 2-5-8 Sumitomo Bakelite Co., Ltd.

Claims (4)

[Claims] 1. 100 parts by weight of a polyamide (A) represented by the general formula (1) and a photosensitive diazoquinone compound (B)
A positive photosensitive resin composition comprising 1 to 100 parts by weight and 1 to 30 parts by weight of a phenol compound (C) represented by the general formula (2). Embedded image Embedded image (Wherein, R ₅ represents a hydrogen atom or an alkyl group;
₆ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ each represent one selected from a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group and a cycloalkyl group. 2. X in the polyamide of the general formula (1)
The positive photosensitive resin composition according to claim 1, wherein is selected from the following. Embedded image 3. Y in the polyamide of the general formula (1)
Is selected from the following: The positive photosensitive resin composition according to claim 1 or 2, wherein Embedded image 4. The positive photosensitive resin composition according to claim 1, wherein the photosensitive diazoquinone compound (B) is selected from the following. Embedded image