JP3078175B2 - 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 having excellent adhesion to a substrate and a sealing resin and excellent solvent resistance.

[0002]

2. Description of the Related Art Conventionally, surface protective films and interlayer insulating films of semiconductor devices have excellent heat resistance and excellent electrical characteristics.
Polyimide resin with mechanical properties etc. is used, but in recent years, the heat resistance cycle has been increased due to higher integration of semiconductor elements, larger size, thinner and smaller sealing resin package, transition to surface mounting method by solder reflow, etc. There is a demand for remarkable improvement in heat resistance, heat shock resistance and the like, and a polyimide resin with higher performance has been required. On the other hand, a technique for imparting photosensitivity to the polyimide resin itself has recently attracted attention. As the photosensitive polyimide resin, for example, the following formula (3)

[0003]

Embedded image

[0004] When this is used, a part of the pattern forming process can be simplified and there is an effect of shortening the process. However, at the time of development, an organic solvent such as N-methyl-2-pyrrolidone is required. There's a problem. 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
In the publication, a positive photosensitive polybenzoxazole precursor comprising a polybenzoxazole precursor and a diazoquinone compound is reported. This is high heat resistance,
In addition to easy processability, it has excellent electrical properties such as low dielectric constant, fine processability, and sensitivity, and has potential as a resin for interlayer insulating films as well as for wafer coat applications. In addition, this positive type photosensitive resin does not require an organic solvent as in the case of other conventional photosensitive polyimide resins, because the removal of the via hole portion is performed using an alkaline aqueous solution, and the work safety is further improved. ing.

However, this photosensitive polybenzoxazole precursor is inferior in adhesion to a substrate, especially a silicon wafer. If the silicon wafer is not pre-treated with a silane coupling agent or the like, it develops during the development or due to moisture absorption after curing. Also has the serious defect of delamination from the substrate. Further, the film after the heat ring closure is slightly poor in elongation and brittle. To overcome these shortcomings,
It is conceivable to introduce an adhesion improving component, a flexibility improving component, etc. into the polymer main chain. However, the synthesis of the actual polybenzoxazole precursor is a reaction between dihydroxydiamine and carboxylic acid dichloride, and the reaction conditions are narrow, and it is very difficult to control the copolymerization in the presence of different components having different reactivities. It is. As another example, JP-A-3-20743 describes a positive photosensitive polybenzoxazole precursor having a hexafluoroisopropylidene group. By showing high solubility in commonly used organic solvents in this photosensitive resin, sensitivity,
Storage stability is improved. However, even the positive polybenzoxazole precursor having a hexafluoroisopropylidene group has insufficient adhesion to a silicon wafer, and peeling occurs in the evaluation of moisture resistance adhesion after curing.

To improve the adhesion, Japanese Patent Application Laid-Open No. 4-318
No. 60 proposes a positive polybenzoxazole precursor resin to which a silicone-modified polyamide is added. This positive photosensitive resin shows excellent adhesion to a substrate such as a silicon wafer, and no peeling of the resin or the like is observed at all even after performing a humidity treatment or the like after curing. But,
Since the positive type polybenzoxazole precursor resin has insufficient adhesion to the sealing resin, a semiconductor device is manufactured by using the positive type polybenzoxazole resin as a surface protective film of a semiconductor element, and is subjected to moisture resistance adhesion. When the property evaluation is performed, there is a problem that peeling occurs between the polybenzoxazole precursor resin and the sealing resin. As described above, the positive-type photosensitive polybenzoxazole precursor resin at present has excellent advantages, but also has a number of serious drawbacks, and its use is severely restricted at present.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel positive photosensitive resin composition having excellent adhesiveness to a substrate and a sealing resin and solvent resistance.

[0008]

The present invention provides (A) a polybenzoxazole precursor having a repeating unit represented by the general formula (1):

[0009]

Embedded image

(B) a silicone-modified polyamic acid comprising a silicone diamine and an aromatic dianhydride represented by the general formula (2):

[0011]

Embedded image

(C) In a positive photosensitive resin composition containing a photosensitive quinonediazide compound as an essential component, the mixing ratio of each component is (B) / (A) = (1-100) / by weight ratio.
100, (C) / (A) = (1-100) / 100, which is a positive photosensitive resin composition.

[0013]

The present invention comprises a very high-adhesion polybenzoxazole precursor having the structure of the formula (1), a silicone-modified polyamic acid having a structure of the formula (2), and diazoquinone which is a positive photosensitive agent. The present invention relates to a positive photosensitive resin composition having excellent adhesion to a substrate and a sealing resin and excellent solvent resistance. The polybenzoxazole precursor of the present invention has the general formula (1), and the general formula (4)

[0014]

Embedded image

[0015] Including the structure shown in. The structure shown in the formula (4) can exhibit flexibility by having an ether bond in the molecule. As a result, a polybenzoxazole precursor having high adhesion is obtained.

As the corresponding diaminophenol,
3,3'-diamino-4,4'-dihydroxydiphenyl ether, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,4'-diamino-3,
4'-dihydroxydiphenyl ether and the like. When used, they may be used alone or as a mixture of two or more. For example, 3,3'-diamino-4,4 '
A polybenzoxazole precursor using dihydroxydiphenyl ether is disclosed in Japanese Patent Publication No. 1-46862. However, this polybenzoxazole precursor and naphthoquinonediazide, a positive-type photosensitive agent,
The positive photosensitive resin composition composed of the components has poor adhesion to, for example, a silicon wafer as a substrate, and peels off during development or during humidity treatment after curing. The present invention is characterized in that the structure of the formula (5) in the general formula (1) is essential for improving the adhesion.

[0017]

Embedded image

The corresponding acids are diphenyl ether-3,3'-dicarboxylic acid, diphenyl ether-
3,4′-dicarboxylic acid, diphenyl ether-4,
4'-dicarboxylic acid, isophthalic acid, benzophenone-
3,3′-dicarboxylic acid, benzophenone-3,4′-dicarboxylic acid, benzophenone-4,4′-dicarboxylic acid, diphenylsulfone-3,3′-dicarboxylic acid, diphenylsulfone-3,4′-dicarboxylic acid, And diphenylsulfone-4,4'-dicarboxylic acid.
Among these acids, isophthalic acid or a dicarboxylic acid having a diphenyl ether group has a very flexible structure and therefore exhibits excellent adhesion. A dicarboxylic acid having a benzophenone group or a diphenylsulfone group exhibits excellent adhesion due to its polar group. These dicarboxylic acids may be used alone or in a mixture of two or more. Terephthalic acid may be used as the dicarboxylic acid component as long as the adhesion does not decrease. In preparing the polybenzoxazole precursor, these dicarboxylic acids are used in the form of dicarboxylic dichloride or an active ester of dicarboxylic acid.

Regarding a specific production method, when dicarboxylic acid dichloride is used, bisaminophenol and pyridine or triethylamine as a catalyst are dissolved in an appropriate solvent in advance, and the dicarboxylic acid dichloride dissolved in the solvent is added. Can be manufactured. When used in the form of an active ester of a dicarboxylic acid, the dicarboxylic acid and the N-hydroxysuccinimide or 1-hydroxybenzotriazole are previously converted to a dicarboxylic acid ester in a suitable solvent using a condensing agent such as carbodiimide. After synthesis, it can be prepared by adding bisaminophenol. As a solvent that can be used in these productions, a solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, dimethylformamide, dimethylsulfoxide, and γ-butyrolactone can be used. In the present invention, it is essential to add a silicone-modified polyamic acid comprising a silicone diamine represented by the general formula (2) and an aromatic dianhydride in order to improve adhesion to a semiconductor chip. As this silicone diamine, for example,

[0020]

Embedded image

And the like. These compounds may be used alone or in combination of two or more. In addition to these silicone diamines, the following aromatic diamines may be used in combination as long as the adhesion is not significantly reduced.

For example, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-
Methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-chloro-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-bromo-4- (4 -Aminophenoxy) phenyl] propane, 2,2-bis [3-ethyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-propyl-4- (4-aminophenoxy) phenyl] Propane, 2,2-bis [3-isopropyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3
-Butyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-sec-butyl-4- (4
-Aminophenoxy) phenyl] propane, 2,2-bis [3,5-dimethyl-4- (4-aminophenoxy)
Phenyl] propane, 2,2-bis [3,5-dichloro-4- (4-aminophenoxy) phenyl] propane,
2,2-bis [3,5-dibromo-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-chloro-4- (4-aminophenoxy) -5-methylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [ 3-chloro-4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-bromo-4- (4-aminophenoxy) phenyl] hexafluoropropane,
2,2-bis [3-ethyl-4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-propyl-4- (4-aminophenoxy) phenyl] hexafluoropropane, 2-bis [3-isopropyl-4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-butyl-4-
(4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-sec-butyl-4- (4-
Aminophenoxy) phenyl] hexafluoropropane,
2,2-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-
Bis [3,5-dichloro-4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [3,5-dibromo-4- (4-aminophenoxy) phenyl] hexafluoropropane, 2-bis [3-chloro-4- (4-aminophenoxy) -5-methylphenyl] hexafluoropropane, 1,1-bis [4- (4
-Aminophenoxy) phenyl] ethane, 1,1-bis [3-methyl-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-chloro-4- (4-aminophenoxy) phenyl] Ethane, 1,1-bis [3
-Bromo-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-ethyl-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-propyl-4- ( 4-aminophenoxy) phenyl] ethane, 1,1-bis [3-isopropyl-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-
Butyl-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-sec-butyl-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3,5-dimethyl- 4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3,5-dichloro-4
-(4-aminophenoxy) phenyl] ethane, 1,1
-Bis [3,5-dibromo-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3-chloro-4
-(4-aminophenoxy) -5-methylphenyl] ethane, bis [4- (4-aminophenoxy) phenyl]
Methane, bis [3-methyl-4- (4-aminophenoxy) phenyl] methane, bis [3-chloro-4- (4-
Aminophenoxy) phenyl] methane, bis [3-bromo-4- (4-aminophenoxy) phenyl] methane,
Bis [3-ethyl-4- (4-aminophenoxy) phenyl] methane, bis [3-propyl-4- (4-aminophenoxy) phenyl] methane, bis [3-isopropyl-4- (4-aminophenoxy) Phenyl) methane,
Bis [3-butyl-4- (4-aminophenoxy) phenyl] methane, bis [3-sec-butyl-4- (4-
Aminophenoxy) phenyl] methane, bis [3,5-
Dimethyl-4- (4-aminophenoxy) phenyl] methane, bis [3,5-dichloro-4- (4-aminophenoxy) phenyl] methane, bis [3,5-dibromo-
4- (4-aminophenoxy) phenyl] methane, bis [3-chloro-4- (4-aminophenoxy) -5-methylphenyl] methane, 3,3-bis [4- (4-aminophenoxy) phenyl] Pentane, 1,1-bis [4
-(4-aminophenoxy) phenyl] propane, 3,
3-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] pentane, 1,1-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] propane, 3,3- Bis [3,5-dibromo-4- (4-aminophenoxy) phenyl] pentane, 1,1-bis [3,5-dibromo-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [ 4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] butane,
2,2-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3,5-
Dibromo-4- (4-aminophenoxy) phenyl] butane, 4,4'-diaminodiphenyl ether, 3,
4'-diaminodiphenyl ether, 1,3-bis (3
-Aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, bis [4- ( 4-aminophenoxy) phenyl] ether and the like can be used in combination.

The aromatic dianhydride used for the silicone-modified polyamic acid includes, for example, pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 4,4'- Oxydiphthalic dianhydride,
3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic acid Dianhydride, naphthalene-2,3
6,7-tetracarboxylic dianhydride, naphthalene-1,
2,5,6-tetracarboxylic dianhydride, naphthalene-
1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride,
4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5 , 6,7-
Hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,
4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-
1,4,5,8-tetracarboxylic dianhydride, 1,4
5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride, 2,2 ′, 3,3 ′ −
Diphenyltetracarboxylic dianhydride, 2,3,3 ′,
4'-diphenyltetracarboxylic dianhydride, 3,
3 ", 4,4" -p-terphenyltetracarboxylic dianhydride, 2,2 ", 3,3" -p-terphenyltetracarboxylic dianhydride, 2,3,3 ", 4"- p-terphenyltetracarboxylic dianhydride, 2,2-bis (2,
3-dicarboxyphenyl) -propane dianhydride, 2,
2-bis (3,4-dicarboxyphenyl) -propane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl)
Ether dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, Bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3
-Dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride,
Perylene-2,3,8,9-tetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride , Perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8
-Tetracarboxylic dianhydride, phenanthrene-1,
2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine 2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, etc. But are not limited to these.

The amount of the silicone-modified polyamic acid (B) is preferably 1 to 100 parts by weight based on 100 parts by weight of the polybenzoxazole precursor (A) represented by the formula (1). If the amount is less than 1 part by weight, the adhesion after the humidity treatment is inferior. If the amount is more than 100 parts by weight, the solubility of the resin in the developer becomes high, and a good pattern cannot be obtained.
Further, in the present invention, a part of the carboxyl group may be imidized by heating the silicone-modified polyamic acid and then used. The photosensitive quinonediazide compound (C) used in the present invention is 1,2-benzoquinonediazide or 1,2-benzoquinonediazide.
A compound having a 2-naphthoquinonediazide structure,
U.S. Pat. Nos. 2,772,972, 2,797,2
No. 13, No. 3,669,658. For example,

[0025]

Embedded image

[0026]

Embedded image

The examples are not limited to these. In addition, when used alone, 2
Mixtures of more than one type may be used. . The blending amount of the photosensitive quinonediazide compound (C) with the polybenzoxazole precursor (A) is as follows.
If the amount is 1 to 100 parts by weight, and if the amount is less than 1 part by weight, the photo-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 include 2,6-dimethyl-3,5-diacetyl-4- (2'-nitrophenyl) -1,4-dihydropyridine, 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. The positive photosensitive resin composition of the present invention may contain a leveling agent and an additive such as a silane coupling agent for further improving the adhesion.

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, etc. are 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
It is performed by spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, or 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 developing solution. 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; 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 and an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as an alcohol such as methanol or ethanol or a surfactant to the aqueous solution 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. Example 1 Synthesis of Polybenzoxazole Precursor 36.4% by weight of 3,3′-diamino-4,4′-dihydroxydiphenyl ether (0.20 mol) was dissolved in 200 parts by weight of dried dimethylacetamide, and 39.6% by weight of pyridine. After adding 0.1 parts by weight (0.50 mol), a solution prepared by dissolving 64.9 parts by weight (0.22 mol) of diphenyl ether-4,4′-dicarboxylic acid chloride in 110 parts by weight of cyclohexanone at −15 ° C. under a stream of dry nitrogen. 3
Add dropwise over 0 minutes. After completion of the dropwise addition, the temperature is returned to room temperature, and stirring is continued for 5 hours under a stream of dry nitrogen. After completion of the reaction, distilled water 7
The precipitate was collected by filtration and dried under reduced pressure to obtain a polybenzoxazole precursor. Synthesis of silicone-modified polyamic acid 1,3-bis (3-aminopropyl) -1,1,3,3
-44.7 parts by weight of tetramethyldisiloxane (0.18
mol) and 61.2 parts by weight (0.19 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride
In 400 parts by weight of N-methyl-2-pyrrolidone,
Stirred at room temperature for 5 hours. The reaction solution was poured into distilled water to obtain a precipitate, which was collected by filtration and dried at 40 ° C. under vacuum. Preparation of photosensitive resin composition 100 parts by weight of synthesized polybenzoxazole precursor,
20 parts by weight of a silicone-modified polyamic acid and 20 parts by weight of a photosensitive diazoquinone compound of the formula (6)

[0032]

Embedded image

Was dissolved in 200 parts by weight of N-methyl-2-pyrrolidone and filtered through a 0.2 μm Teflon filter to obtain a photosensitive varnish. Characteristic evaluation This photosensitive varnish is applied on a silicon wafer using a spin coater and dried in an oven at 70 ° C. for 1 hour to obtain a coating film having a thickness of about 6 μm. A mask manufactured by Toppan Printing Co., Ltd. (Test chart No. 1; width: 50 to 0.88 μm)
m is drawn with an ultraviolet ray from a high-pressure mercury lamp through which 0.7
6% in 9% tetramethylammonium hydroxide aqueous solution
After the exposed portion was dissolved and removed by immersion for 0 second, the developing solution was washed away with water for 30 seconds (rinse). as a result,
A fine coating film pattern with a thickness of 5.8 μm is formed on the silicon wafer, and the width of the minimum remaining pattern that does not cause peeling from the wafer (hereinafter, this value is referred to as “adhesion during development”) is as small as 5 μm. It was confirmed that peeling of the coating film during development was also suppressed in the pattern.

In addition, a photosensitive varnish is separately coated on a silicon wafer in the same manner, 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. The obtained coating film was cut into 100 squares on a 1 mm square, a cellophane tape was stuck and peeled off, and the coating film was to be peeled off from the silicon wafer. (Referred to as “peeling number”) was 0, and it was confirmed that the cured film had excellent adhesion to the wafer. Further, after applying and curing this photosensitive varnish on a silicon wafer in the same manner as described above, an epoxy resin composition for semiconductor encapsulation (manufactured by Sumitomo Bakelite Co., Ltd., EME-630) is formed on the cured film.
0H) was formed into a size of 2 mm × 2 mm × 2 mm (width × length × height). The sealing epoxy resin composition molded on the cured polybenzoxazole resin film was peeled off using Tensilon, and the shear strength was measured. 3.2
kg / mm ² . Separately, a photosensitive varnish was similarly applied to a silicon wafer, prebaked, and cured by heating. The obtained silicon wafer was immersed in a stripping solution 105 manufactured by Tokyo Ohka Co., Ltd. at 50 ° C. for 3 minutes, rinsed with isopropyl alcohol and air-dried, and the surface was observed. Met. In this way, a resin capable of forming a fine pattern and having excellent adhesion and solvent resistance was obtained.

Judgment Criteria for Characteristic Evaluation Adhesion at Development: The smaller the minimum pattern size peeled during development, the higher the adhesion. Peeling number after curing: The smaller the number of peeled patterns in the cellophane test after curing, the higher the adhesion. Shear strength: indicates the adhesiveness with the epoxy resin composition for semiconductor encapsulation, and the larger the value, the higher the adhesiveness. Solvent resistance: Change in appearance of the film after dipping the cured film in a stripping solution.

Examples 2 to 5 In Example 1, 50 mol% of diphenyl ether-4,4'-dicarboxylic acid dichloride as an acid component of the polybenzoxazole precursor was converted to isophthalic acid dichloride (Example 2). Instead of the acid component of the benzoxazole precursor, benzophenone-4,4′-dicarboxylic acid dichloride (Example 3), and the amine component 1,3-bis (3-aminopropyl)-of the silicone-modified polyamic acid in Example 1 10 mol% of 1,1,3,3-tetramethyldisiloxane is converted to 4-4′-diaminodiphenyl ether (Example 4), and similarly, 3,3 ′, 4,4 ′ of the acid component of the silicone-modified polyamic acid. -50 mol% of benzophenonetetracarboxylic dianhydride
Was evaluated as the same as 4,4′-oxydiphthalic dianhydride (Example 5). Examples 2 to 5 and Comparative Example 1
Also in Examples 10 to 10, as in Example 1, 20 parts by weight of the photosensitive diazoquinone compound of the formula (6) was dissolved in 200 parts by weight of N-methyl-2-pyrrolidone with respect to 100 parts by weight of the polybenzoxazole precursor. did. Table 1 shows the evaluation results.

Comparative Examples 1 and 2 Terephthalic acid dichloride (Comparative Example 1) was used in place of diphenyl ether-4,4'-dicarboxylic acid dichloride as the acid component of the polybenzoxazole precursor in Example 1.
In addition, 1,1 of the amine component of the silicone-modified polyamic acid
The same evaluation was performed by replacing 4,4 -'- diaminodiphenyl ether (Comparative Example 2) with 3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane. Table 2 shows the evaluation results. Comparative Example 3 The same evaluation was carried out without adding the silicone-modified polyamic acid in Example 1 (Comparative Example 3). Table 2 shows the evaluation results. Comparative Example 4 The acid component 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride of the silicone-modified polyamic acid in Example 1 was replaced with 3,3', 4,4'-biphenyltetracarboxylic dianhydride The same evaluation was performed by changing to the object. Table 2 shows the evaluation results. Comparative Example 5 3,3′-diamino-4,4′-dihydroxydiphenyl ether as an amine component of the polybenzoxazole precursor in Example 1 was replaced with 2,2-bis (3-amino-4
-Hydroxyphenyl) hexafluoropropane and diphenyl ether-4,4'-dicarboxylic acid dichloride as an acid component was changed to isophthalic dichloride / terephthalic acid = 50/50 mol%, and the same evaluation was performed.
Table 2 shows the evaluation results.

Comparative Example 6 3,3'-diamino-4,4'-dihydroxydiphenyl ether as an amine component of the polybenzoxazole precursor in Example 1 was replaced with 4,4'-diamino-3,3'-diamine.
The same evaluation as in Example 1 was performed without using silicone-modified polyamic acid instead of dihydroxybiphenyl. Table 3 shows the evaluation results. Comparative Example 7 The 3,3′-diamino-4,4′-dihydroxydiphenyl ether as the amine component of the polybenzoxazole precursor in Example 1 was replaced with 4,4′-diamino-3,3′-
The same evaluation as in Example 1 was performed instead of dihydroxybiphenyl. Table 3 shows the evaluation results.

Comparative Example 8 3,3′-Diamino-4,4′-dihydroxydiphenyl ether as an amine component of the polybenzoxazole precursor in Example 1 was converted to 2,2-bis (3-amino-4-
Hydroxyphenyl) hexafluoropropane,
Further, the same evaluation as in Example 1 was performed without adding the silicone-modified polyamic acid. Table 3 shows the evaluation results. Comparative Example 9 3,3′-diamino-4,4′-dihydroxydiphenyl ether as an amine component of the polybenzoxazole precursor in Example 1 was converted to 2,2-bis (3-amino-4-
Hydroxyphenyl) hexafluoropropane,
The same evaluation as in Example 1 was performed. Table 3 shows the evaluation results. Comparative Example 10 The same evaluation was performed with the addition amount of the silicone-modified polyamic acid used in Example 1 reduced to 0.5 part by weight. Table 3 shows the evaluation results.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

According to the present invention, it is possible to obtain a positive photosensitive resin composition having excellent solvent resistance and excellent adhesion to a substrate and a sealing resin.

──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 79/08 C08G 73/22 CA (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. A polybenzoxazole precursor having a repeating unit represented by the general formula (1): (B) a silicone-modified polyamic acid comprising a silicone diamine represented by the general formula (2) and an aromatic dianhydride; and (C) In a positive photosensitive resin composition containing a photosensitive quinonediazide compound as an essential component, the mixing ratio of each component is (B) / (A) = (1 to 100) / 100 in weight ratio;
(C) / (A) = (1-100) / 100, wherein the positive photosensitive resin composition is characterized in that: 2. The polybenzoxazole precursor having a repeating unit represented by the general formula (1), wherein R ₁ has the following structure: The positive photosensitive resin composition according to claim 1. 3. The positive photosensitive resin composition according to claim 1, wherein the polybenzoxazole precursor having a repeating unit represented by the general formula (1) has the following structure. Embedded image 4. The aromatic acid dianhydride constituting the silicone-modified polyamic acid is 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 4,4'-oxydiphthalic dianhydride. Claim 1, Claim 2 or Claim 3
The positive photosensitive resin composition according to the above. 5. The silicone diamine represented by the general formula (2) is 1,3-bis (3-aminopropyl) -1,1,1
5. The positive photosensitive resin composition according to claim 1, which is 3,3-tetramethyldisiloxane. 6. The method of claim 1, wherein the photosensitive quinonediazide compound is 1- [1
-(4-hydroxyphenyl) isopropyl] -4-
6. An esterified product of [1,1-bis (4-hydroxyphenyl) ethyl] benzene and 1,2-naphthoquinonediazidesulfonic acid chloride, claim 1, claim 2, claim 3, claim 4, or claim 5. The positive photosensitive resin composition according to the above.