JPH11119426A - Positive photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a positive photosensitive resin composition superior in adhesion and transparence and high in sensitivity by using a specified polybenzoxazole precursor and, as a photosensitive diazonaphthoquinone compound, a reaction product of a specified component and a phenol compound, as essential components. SOLUTION: The positive photosensitive resin composition is composed essentially of a polybenzoxazole precursor represented by formula I and, as the photosensitive diazonaphthoquinone compound, the reaction product of a component represented by formula II and a phenol compound, and in the formula I, (n) is an integer of 2-200. This polybenzoxazole precursor can be obtained by condensing 3,3'-diamino-4,4'-dihydroxy-diphenylsulfone with a dicarboxylic acid having an R structure, and the photosensitive azoquinone compound can be embodied by the esterified product of trihydroxybenzophenone and 1,2- naphthoquinediazide-5-sulfochloride and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive-type photosensitive resin composition which is excellent in transparency at the time of exposure and can provide a pattern having high sensitivity and excellent adhesion.

[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, there is a photosensitive polyimide resin that has recently attracted attention for a technique of imparting photosensitivity to the polyimide resin itself.

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 are problems 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 not only for wafer coating but also as a resin for interlayer insulation. In addition, since the positive type photosensitive resin uses an alkaline aqueous solution to remove the via hole, an organic solvent is not required for development unlike the conventional photosensitive polyimide, so that safety during operation is further improved. ing. However, this photosensitive polybenzoxazole resin absorbs light at wavelengths in the low wavelength region and is not sufficiently transparent, so that the sensitivity is insufficient particularly when using actinic radiation in the low wavelength region or when forming a thick film. was there.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high-sensitivity positive photosensitive resin having excellent adhesiveness and excellent transparency.

[0005]

According to the present invention, there is provided a positive photosensitive resin composition comprising, as essential components, a polybenzoxazole precursor (A) and a reaction product of a component (B) and a phenol compound as a photosensitive diazonaphthoquinone compound. In particular, the polybenzoxazole precursor is represented by the formula (C).

[0006]

Embedded image n is an integer from 2 to 100, and R is a group selected from the group shown below.

[0007]

Embedded image Here, X is a group selected from the following groups.

[0008]

Embedded image O and p each represent an integer of 4 to 20, and q and r each represent an integer of 1 to 20. Y represents an alkyl group or a phenyl group, each being independently selected from each other.

[0009]

Embedded image

Further, R of the polybenzoxazole precursor (A) is preferably a group selected from the following groups.

[0011]

Embedded image Here, X represents the following structure.

[0012]

Embedded image Also, o and p each represent an integer from 4 to 20, and q and r each represent an integer from 1 to 20. Y represents an alkyl group or a phenyl group, each being independently selected from each other.

[0013]

Embedded image Here, Q shows the following formula, and s and t show the integer of 1-99.

[0014]

Embedded image R ′ and R ″ are each a group selected from the following groups and are not the same as each other.

[0015]

Embedded image Here, X is a group selected from the following groups.

[0016]

Embedded image O and p each represent an integer from 4 to 20, and q and r represent 1
Indicates an integer from to 20. Y represents an alkyl group or a phenyl group, each being independently selected from each other.

[0017]

Embedded image

Further, R ′ and R ″ of the polybenzoxazole precursor (C) are preferably groups selected from the following groups.

[0019]

Embedded image Here, X is a group selected from the following group.

[0020]

Embedded image Also, o and p each represent an integer from 4 to 20, and q and r each represent an integer from 1 to 20. Y represents an alkyl group or a phenyl group, each being independently selected from each other.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The process for producing a polybenzoxazole precursor according to the present invention comprises the steps of preparing a 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone and a dicarboxylic acid having the structure of R by a conventional acid chloride method, And condensation in the presence of a dehydrating condensing agent such as dicyclohexyldicarbodiimide or the like.

The diazoquinone compound used as the light-sensitive component of the present invention may be 1,2 naphthoquinonediazide or
A compound having 1,2-benzoquinonediazide,
These photosensitive compounds are described in U.S. Pat.
No. 72,972, No. 2,797,213, No. 3,66
No. 9,658 and the like. Also, photosensitive diazoquinone is a known substance used in the field of positive resists as disclosed and disclosed in Japanese Patent Publication No. 3-158856. Examples of the phenol compound include bisphenol A, bisphenol F, and trihydroxybenzophenone, and various phenol compounds used for novolak resin resists. For example, trihydroxybenzophenone and 1,2-naphthoquinonediazido-5
Examples thereof include esterified products of sulfonic acid chloride.
Such a diazoquinone compound itself is a substance that is hardly soluble in an aqueous alkaline solution, but generates a carboxyl group upon exposure to light and becomes easily soluble in an aqueous alkaline solution.

In addition, additives such as a leveling agent and a silane coupling agent can be added to the positive photosensitive resin composition of 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, 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, etc. May be used alone or in combination of two or more.

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 silicone wafer or a ceramic 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 alcohols such as methanol and 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 for interlayer insulation of multilayer circuits, cover coats of flexible guide plates, solder resist films, liquid crystal alignment films, and the like.

[0026]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which by no means limit the scope of the present invention. The following parts indicate parts by weight.

Example 1 3,3'-Diamino-4
56 parts of 4 'dihydroxydiphenyl sulfone (0.2
mol) was dissolved in 200 parts of dry dimethylacetamide, and 39.6 parts (0.5 mol) of pyridine were added.
Under dry nitrogen at −15 ° C., 100 parts of cyclohexane
60.3 parts (0.14 mol) of 4'-hexafluoroisopropylidenedibenzoyl chloride and 11.8 parts of 4,4'-oxybisbenzoyl chloride (0.04 m
ol) was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was returned to room temperature and stirred at room temperature for 5 hours. afterwards,
The reaction solution was dropped into 7 liters of distilled water, and the precipitate was collected and dried to obtain a polybenzoxazole precursor.

This polybenzoxazole precursor 100
Parts of trihydroxybenzophenone and 12 parts of a reaction product of naphthoquinonediazido 5-sulfonic acid chloride as a photosensitive agent were dissolved in 200 parts of γ-butyrolactone,
The mixture was filtered through a μm Teflon filter to obtain a photosensitive varnish.

The photosensitive varnish was applied on a silicon wafer by using a spray coater, and then applied in an oven.
After drying at ℃ 1 hour, a coating film having a thickness of 5 μm was obtained. A mask manufactured by Toppan Printing Co., Ltd. (Test Chart No. 1;
A high-pressure mercury lamp was used to change the amount of exposure to ultraviolet light, and the irradiation was performed using a high-pressure mercury lamp. Next, the exposed portion was dissolved and removed by immersion in a 0.79% aqueous solution of tetramethylammonium hydroxide for 30 seconds, and then rinsed with pure water for 30 seconds. As a result, the exposed portion was completely dissolved by irradiation at an exposure amount of 170 mJ / cm2,
J / cm2), and a good pattern was formed. At this time, the film thickness after development was 4.1 μm, and the residual film ratio was 82.
0% (film thickness after development / film thickness before development × 100 = 4.1 μ)
m / 5.0 μm × 100 = 82.0%). Separately, a photosensitive varnish was similarly coated on a silicon wafer, prebaked, and then placed in an oven at 150 ° C. /
The resin was heated and cured in the order of 30 minutes, 250 ° C./30 minutes, and 350 ° C./30 minutes. The obtained coating film was cut into 100 squares in a square of 1 mm, a cellophane tape was stuck and peeled off, and the coating film was to be peeled off from the silicon wafer. (Referred to as “film adhesion”) was 0, and it was confirmed that the adhesion of the cured film to the wafer was excellent.

Example 2 The photosensitive varnish of Example 1 was applied on a silicon wafer using a spray coater, and then dried in an oven at 70 ° C. for 1 hour to obtain a coating film having a thickness of 5 μm. Varnish was applied on a silicon wafer using a spray coater, and then applied in an oven.
C. for 1 hour to obtain a coating film having a thickness of 10 .mu.m.
The evaluation was performed in the same manner as described above.

Example 3 4,4'-Hexafluoroisopropylidene dibenzoyl chloride 6 of Example 1
Instead of 0.3 part (0.14 mol) and 11.8 parts (0.04 mol) of 4,4'-oxybisbenzoyl chloride, 77.6 parts (0.4%) of 4,4'-hexafluoroisopropylidene dibenzoyl chloride. 18 mol) in the same manner as in Example 1.

Example 4 4,4'-Hexafluoroisopropylidene dibenzoyl chloride 6 of Example 1
Instead of 0.3 part (0.14 mol) and 11.8 parts (0.04 mol) of 4,4'-oxybisbenzoyl chloride, 60.3 parts of 4,4'-hexafluoroisopropylidene dibenzoyl chloride (0. 14 mol) and 1.428 cyclohexyldicarboxylic acid chloride 8.28
The evaluation was performed in the same manner as in Example 1 using parts (0.04 mol).

COMPARATIVE EXAMPLE 1 Instead of 56 parts (0.2 mol) of 3,3'-diamino-4,4'-dihydroxydiphenylsulfone of Example 1, 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoro Evaluation was performed in the same manner as in Example 1 using 73.3 parts (0.2 mol) of propane.

Comparative Example 2 Instead of 56 parts (0.2 mol) of 3,3′-diamino-4,4′-dihydroxydiphenylsulfone in Example 1, 43.2 parts (0.2 mol) of 3,3′-dihydroxybenzidine were used. ) Was evaluated in the same manner as in Example 1.

[0035]

[Table 1]

[0036]

According to the photosensitive photosensitive resin of the present invention, adhesion and transparency are improved and high sensitivity is achieved by having a sulfone type bond in the skeleton of the polybenzoxazole resin. is there.

Claims (4)

[Claims] 1. A polybenzoxazole precursor (A) represented by the following formula, and (B) a photosensitive diazonaphthoquinone compound
A positive photosensitive resin composition comprising, as an essential component, a reaction product of a component and a phenol compound. Embedded image n is an integer from 2 to 100, and R is a group selected from the group shown below. Embedded image Here, X is a group selected from the following groups. Embedded image O and p each represent an integer of 4 to 20, and q and r each represent an integer of 1 to 20. Y represents an alkyl group or a phenyl group, each being independently selected from each other. Embedded image 2. A polybenzoxazole precursor (C) represented by the following formula, and (B) a photosensitive diazonaphthoquinone compound
A positive photosensitive resin composition comprising, as an essential component, a reaction product of a component and a phenol compound. Embedded image Here, Q shows the following formula, and s and t show the integer of 1-99. Embedded image R ′ and R ″ are each a group selected from the following groups, and are not the same as each other. Here, X is a group selected from the following groups. Embedded image O and p each represent an integer from 4 to 20, and q and r represent 1
Indicates an integer from to 20. Y represents an alkyl group or a phenyl group, each being independently selected from each other. Embedded image 3. The positive photosensitive resin composition according to claim 1, wherein R of the polybenzoxazole precursor (A) is a group selected from the following group. Embedded image Here, X represents the following structure. Embedded image Also, o and p each represent an integer from 4 to 20, and q and r each represent an integer from 1 to 20. Y represents an alkyl group or a phenyl group, each being independently selected from each other. 4. The positive photosensitive resin composition according to claim 2, wherein R ′ and R ″ of the polybenzoxazole precursor (C) are groups selected from the following group: Here, X is a group selected from the following group. Embedded image Also, o and p each represent an integer from 4 to 20, and q and r each represent an integer from 1 to 20. Y represents an alkyl group or a phenyl group, each being independently selected from each other.