JPH1184645A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive resin composition superior in photosensitive and resolution and film endurance and unnecessary for heating at high temperature and advantageous from the view point of safety and environment maintenance and developable in an aqueous solution of alkal by using a combination of a specified polyimide resin and a photosensitive diazoquinone compound. SOLUTION: This resin composition comprises at least the polyimide resin composed of structural units represented by the formula and the photosensitive diazoquinone compound. In the formula, X is a tetravalent organic group. 2-100 pts.wt. of this diazoquinone compound is mixed with 100 pts.wt. of the resin. The photosensitive diazoquinone compound is an o-naphthoquinondiazidosulfonic acid derivative. Acid dianhydrides for composing the polyimide resin is 2,2-bis(3,4 dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydrides. The polyimide resin can be prepared with a dmiamine compound and tetracarboxylic acid dianhydrides.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition which is effectively used for applications such as a protective insulating film for a semiconductor device, an alignment film for a liquid crystal display device, and an insulating film for a multilayer printed circuit board. In particular, it relates to a heat-resistant protective film for electronic parts obtained by curing the composition.

[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, thinning and miniaturization of the encapsulation resin package, and the shift to surface mounting by solder reflow. It has come to be.

On the other hand, in recent years, a technique of a so-called photosensitive polyimide, in which a part of a pattern forming process can be simplified and the process can be shortened, is imparted with a photosensitivity to a polyimide resin itself, has attracted attention. For example, JP-A-49-11554
No. 1 and JP-A-55-45746 disclose a material comprising a carboxyl group of a polyamic acid having a photosensitive group introduced through an ester bond.
No. 143 proposes a material comprising a photosensitive group introduced into a carboxyl group of a polyamic acid by an amide bond, and the like. However, these materials have a problem that the film swells at the time of development, and that at the time of development, N-methyl-
Since an organic solvent such as 2-pyrrolidone is required, there has been a problem that enormous equipment and the like are required for its management in terms of safety and environment.

Therefore, in recent years, a positive photosensitive resin which can be developed with an alkaline aqueous solution has been developed. For example, JP-A-2-181149 proposes a photosensitive resin composition comprising an esterified polyamic acid polymer and a photosensitive quinonediazide. This photosensitive resin composition,
Since the removal of the via hole is performed using an aqueous alkaline solution, no organic solvent is required for development unlike the conventional photosensitive polyimide resin, so it is very advantageous in terms of safety and environmental measures at the time of work etc. Has become.

[0005]

However, all of the above-mentioned conventional photosensitive polyimide resins are obtained by imparting photosensitivity to polyamic acid, which is a precursor of the polyimide resin, and finally converted from the polyamic acid to the polyimide resin. (Imidization) requires heat treatment at a high temperature of 300 ° C. or more, and can be used only on a substrate or an element that can withstand this heat;
In addition, the pattern obtained at the time of imidization has a large dimensional change such as volume shrinkage due to heat, and there is a problem in dimensional stability.

The present invention solves the above-mentioned problems of the prior art, and an object of the present invention is to provide an alkaline aqueous solution which is free from swelling in a film at the time of development, is safe in operation, and is superior in environmental problems. It is another object of the present invention to provide a novel photosensitive resin composition which can be developed by using a photosensitive resin composition and does not require heat treatment with high heat.

[0007]

Means for Solving the Problems In order to achieve the above object in the present invention, first, in the invention of claim 1, at least a polyimide resin (A) comprising a structural unit represented by the above general formula (1) ) And a photosensitive diazoquinone compound (B)
And a photosensitive resin composition characterized by containing

In the invention of claim 2, the photosensitive diazoquinone compound (B) is a polyimide resin (A) 10
A photosensitive resin composition characterized by being blended in an amount of 2 to 100 parts by weight per 0 parts by weight.

According to a third aspect of the present invention, there is provided a photosensitive resin composition wherein the photosensitive diazoquinone compound (B) is an o-naphthoquinonediazidosulfonic acid derivative.

In the invention of claim 4, the acid dianhydride constituting the polyimide resin (A) is 2,2-bis (3,2
4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride.

[0011]

Embodiments of the present invention will be described below in detail. The photosensitive resin composition of the present invention, at least,
It is characterized by containing a polyimide resin (A) comprising a structural unit represented by the general formula (1) and a photosensitive diazoquinone compound (B), and the polyimide resin (A) For example, it can be easily produced from a diamine compound and a tetracarboxylic dianhydride.

The above diamine compound refers to 4,4'-diamino-4 "-hydroxytriphenylamine. This diamine can be easily produced, for example, using p-halonitrobenzene and 4-benzyloxyaniline as starting materials. As a specific example, 4-benzyloxyaniline and p-chlorobenzene are mixed with dimethyl sulfoxide in 10%.
It is obtained by reacting at 0 ° C., recrystallizing the obtained compound, and then performing reduction and deprotection.

The tetracarboxylic dianhydride represented by the general formula (1) includes pyromellitic dianhydride, 3, 4,
3 ', 4'-biphenyltetracarboxylic dianhydride, 3,
4,3 ', 4'-diphenylethertetracarboxylic dianhydride, 3,4,3', 4'-benzophenonetetracarboxylic dianhydride, 3,4,3 ', 4'-diphenylsulfonetetracarboxylic dianhydride Anhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 3,4,3 ", 4" -terphenyltetra Examples thereof include tetracarboxylic dianhydrides such as carboxylic dianhydride. These tetracarboxylic acids may be used alone or in combination of two or more.

An example of the method for producing a polyimide resin according to the present invention is as follows. A polyamic acid is prepared by reacting a diamine compound with a tetracarboxylic dianhydride in an organic solvent at -20 to 50 ° C. for several minutes to several days. And then heating or treating with a dehydrating ring-closing agent to obtain a polyimide resin. Organic solvents that can be used in the synthesis reaction of this polyamic acid include N, N-dimethylacetamide, N
Amide solvents such as -methyl-2-pyrrolidone, benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile, aromatic solvents such as pyridine,
Examples thereof include halogen solvents such as chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, and ether solvents such as tetrahydrofuran, dioxane and diglyme. Especially
When an amide solvent such as N, N-dimethylacetamide or N-methyl-2-pyrrolidone is used, a high-polymer polyamic acid can be obtained.

The polyamic acid obtained as described above is then dehydrated and ring-closed to obtain a polyimide resin. A known method can be used for the dehydration and ring closure method. For example, a thermal cyclization method by refluxing toluene, xylene, or the like can be used. Since this polyimide resin contains toluene, xylene and the like used for dehydration, water, a polyimide resin solution is poured into a poor solvent such as methanol, reprecipitated, and further dried to obtain a powder of the polyimide resin. I do. This is dissolved in a desired organic solvent to obtain a solution of a soluble polyimide resin used in the present invention.

The molecular weight of the polyimide resin of the present invention in this method is limited by the amount charged with the diamine compound, and a high molecular weight polyimide resin can be produced when used in equimolar amounts.

In the present invention, examples of the photosensitive diazoquinone compound (B) used in combination with the above-mentioned polyimide resin (A) include o-naphthoquinonediazidesulfonic acid ester and o-naphthoquinonediazidosulfonamide. In the present invention, the following general formula (2)

[0018]

Embedded image (Wherein, Y represents a monovalent organic group containing an aromatic ring), and o-naphthoquinonediazidosulfonic acid ester represented by the following formula is preferable.

Specific examples of the o-naphthoquinonediazidosulfonic acid ester represented by the general formula (2) are not limited thereto, but correspond to the following (Chemical Formula 3) to (Chemical Formula 11). General formulas (3) to (11)

[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

Embedded image (However, Z in the formulas 8 to 11 represents a general formula (Formula 12))

[0029]

Embedded image Can be exemplified, these can be used alone or 2
It can be used in combinations of more than one species.

The photosensitive resin composition of the present invention can be obtained by mixing the above-mentioned polyimide resin (A) represented by the general formula (1) with the photosensitive diazoquinone compound (B). The mixing ratio of the two is optional, but in order to obtain good photosensitivity and storage stability, the polyimide resin (A) 10
The photosensitive diazoquinone compound is used in an amount of 2-1 to 0 parts by weight.
It is preferred to use it in an amount of 00 parts by weight, especially 5 to 50 parts by weight.

The photosensitive resin composition of the present invention is generally used in a form dissolved in an appropriate organic solvent, and is applied to a substrate. The solvent used here is N-methyl-2
-Pyrrolidone, N, N-dimethylacetamide, γ-butyrolactone, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like may be 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 application method is
Spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like are performed. 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; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine , An aqueous solution of alkalis such as quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and an appropriate amount of a water-soluble organic solvent or a surfactant such as alcohols such as methanol and ethanol. The used aqueous solution can be suitably used. As a developing method, a method 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, a heat treatment is performed to obtain a final pattern having high heat resistance.

The photosensitive resin composition according to the present invention can easily form a pattern, and the resin film formed after the heat treatment has excellent heat resistance, mechanical properties, and electrical properties.
Junction coat film, passivation film, buffer coat film, LS on the surface of semiconductor elements such as IC and LSI
It can be suitably used for an α-ray blocking film such as I., 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.

[0036]

The present invention will be described in more detail with reference to the following examples. <Example 1> [Synthesis of polyimide (A)] 0.595 g of 4,4'-diamino-4 "-hydroxytriphenylamine (0.020 m
ol) was dissolved in 10 ml of N-methyl-2-pyrrolidone, and 0.601 g (0.020 mol) of 2,2 was added thereto.
-Bis (3,4-dicarboxyphenyl) -1,1,1,3
3,3-Hexafluoropropane dianhydride was added all at once as a solid. After stirring at 25 ° C. for 12 hours, the mixture was poured into a mixed solution of water and methanol, then filtered, and further vacuum-dried at 50 ° C. for 12 hours to obtain a polyamic acid. The obtained polyamic acid was dissolved in xylene in 8
The mixture was heated and stirred for an hour to perform imidization. This reaction solution was poured into a large amount of a mixed solution of water and methanol to reprecipitate the polyimide resin, and further dried at 180 ° C. for 12 hours under vacuum to obtain a polyimide resin powder.

[Preparation of photosensitive resin composition] 15 parts by weight of the synthesized polyimide and 5 parts by weight of the photosensitive diazoquinone represented by the above general formula (3) (formula 3) were combined with 80 parts by weight of N-methyl-2-pyrrolidone. And filtered through a 0.2 μm Teflon filter to obtain a photosensitive varnish.

[Evaluation of Characteristics] The photosensitive varnish was applied to a silicon wafer to a thickness of about 5 μm using a spin coater, dried, and then passed through a photomask through a glass filter with an ultra-high pressure mercury lamp to a wavelength of 436 nm. Irradiation with actinic light was performed to perform contact exposure of 200 mJ / cm ² . Subsequently, development was carried out with a 2.5% aqueous solution of tetramethylammonium hydroxide, followed by rinsing with pure water, and the obtained line-and-space pattern shape and the obtained minimum line width were observed. Further, they were subjected to a heat treatment at 200 ° C. for 1 hour, and the residual film ratio to the film thickness before curing was determined. The results are shown in Table 1.

Example 2 Instead of 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 3,4,3 ′ Example 1 except that 4,4'-benzophenonetetracarboxylic dianhydride was used.
Synthesis and pattern formation were performed in the same manner as described above, and the characteristics were evaluated. The results are shown in Table 1.

Example 3 Instead of 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 3,4,3 ′ Synthesis and pattern formation were carried out in the same manner as in Example 1 except that 4,4′-biphenyltetracarboxylic dianhydride was used, and the characteristics were evaluated. The results are shown in Table 1.

Example 4 A photosensitive diazoquinone was synthesized in the same manner as in Example 1 except that the above-mentioned general formula (6) (chemical formula 6) was used instead of the general formula (3) (chemical formula 3). Then, a pattern was formed, and the characteristics were evaluated. The results are shown in Table 1.

<Example 5> A photosensitive diazoquinone was synthesized in the same manner as in Example 1 except that the above-mentioned general formulas (9) and (9) were used instead of the general formulas (3) and (3). Then, a pattern was formed, and the characteristics were evaluated. The results are shown in Table 1.

[0043]

[Table 1]

From the above results, the present invention is excellent in photosensitivity and resolution, does not require heating at high temperature, has excellent residual film properties, and can be developed in an alkaline aqueous solution which is safe for operation. It has been found that a possible photosensitive resin composition can be provided.

[0045]

As described above, the present invention has the following effects. That is, the photosensitive diazoquinone compound comprises at least a polyimide resin comprising a structural unit represented by the above general formula (Chemical Formula 1) and a photosensitive diazoquinone compound, and the photosensitive diazoquinone compound is used in an amount of 2 to 100 parts by weight of the polyimide resin. A photosensitive resin composition formulated in an amount of 100 parts by weight, wherein the photosensitive diazoquinone compound is an o-naphthoquinonediazidosulfonic acid derivative, and the acid dianhydride constituting the polyimide resin is 2,2. Two
-Bis (3,4-dicarboxyphenyl) -1,1,1,3
Because it is a novel photosensitive resin composition characterized by being 3,3-hexafluoropropane dianhydride, excellent photosensitivity, resolution, residual film properties that could not be achieved with the conventional one, and A photosensitive resin composition which does not require heating at a high temperature and which can be developed with an alkaline aqueous solution which is advantageous in terms of work safety and environment is obtained. The polyimide film obtained by heating the photosensitive resin composition can be suitably used as a protective film for electronic parts, and therefore has great value as an industrial material.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01L 21/312 H05K 3/46 T H05K 3/46 H01L 21/30 502R

Claims (4)

[Claims] At least one of the following general formulas (1): (Wherein X represents a tetravalent organic group), comprising a polyimide resin (A) having a structural unit represented by the formula (A) and a photosensitive diazoquinone compound (B). Resin composition. 2. The photosensitive diazoquinone compound (B) is
2 to 100 per 100 parts by weight of the polyimide resin (A)
2. The composition according to claim 1, which is blended in an amount of part by weight.
The photosensitive resin composition as described in the above. 3. The method according to claim 1, wherein the photosensitive diazoquinone compound (B) is
3. The photosensitive resin composition according to claim 1, which is an o-naphthoquinonediazidosulfonic acid derivative. 4. An acid dianhydride constituting said polyimide resin (A) is 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane. 4. The photosensitive resin composition according to claim 1, which is a dianhydride.