JP2854675B2 - Heat-resistant photosensitive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to a heat-resistant photosensitive composition excellent in heat resistance, photosensitivity, storage stability and the like. The heat-resistant photosensitive composition of the present invention is suitable for forming an insulating layer or a passivation layer of a solid-state device.

(Prior Art) In the semiconductor industry, a material having high photosensitivity and high heat resistance is required as a polymer material for forming an insulating layer and a passivation layer of a solid-state element. Conventionally, as a heat-resistant polymer material having photosensitivity, JP-A-49-115541, JP-A-54-116216, JP-A-54-16217, JP-A-56-45915, In Japanese Patent Application Laid-Open No. 54-89623 and the like, polyimides and polyamideimides have been proposed. However, none of these proposed materials was fully satisfactory.

(Problems to be Solved by the Invention) That is, these heat-resistant materials having photosensitivity have insufficient photosensitivity, require high-temperature heating for final curing, and have poor storage stability. It has a large shrinkage and has some disadvantages, and therefore is not always suitable as a material for forming a thick insulating film.

The object of the present invention is to solve these drawbacks and problems, and has both high heat resistance and high sensitivity photopolymerizability, as well as chemical resistance, storage stability, and moisture resistance. An object of the present invention is to provide an excellent novel heat-resistant photosensitive composition.

[Constitution of the Invention] The present inventors have conducted intensive studies to achieve the above object, and as a result, a specific epoxy compound having an imide group,
By using a polyimide resin reacted with a monobasic acid having a photopolymerizable unsaturated group, it is found that heat resistance and photosensitivity, excellent storage stability, etc., and that the above objects are achieved, and the present invention It is completed.

That is, the present invention provides: (a) an epoxy compound having an imide group represented by the following general formula; (Where R is (B) A heat-resistant photosensitive composition comprising: a polyimide resin obtained by reacting a monobasic acid having a photopolymerizable unsaturated group; and a sensitizer or a photopolymerization initiator.

 Hereinafter, the present invention will be described in detail.

The polyimide resin used in the present invention is obtained by subjecting (a) an epoxy compound having an imide group and (b) a monobasic acid having a photopolymerizable unsaturated group to an addition reaction. (A) The epoxy compound having an imide group is represented by the following general formula.

(Where R is (B) Examples of the monobasic acid having a photopolymerizable unsaturated group include methacrylate, methyl methacrylate, and cinnamic acid, and these may be used alone or as a mixture of two or more.

The polyimide resin used in the present invention is prepared by mixing substantially equimolar (a) an epoxy compound having an imide group and (b) a monobasic acid having a photopolymerizable unsaturated group in an organic solvent for 60 to 200 times.
The reaction can be carried out at a temperature of ° C. for 3 to 12 hours. If necessary in this addition reaction, solvents such as N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, dioxane, diglyme and the like can be used. In this reaction, it is desirable to use a basic reaction catalyst such as a tertiary amine.

As the sensitizer or photopolymerization initiator used in the present invention, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin alkyl ethers such as benzoin phenyl ether, benzoin thioethers, benzophenone, acetophenone, 2-ethylanthraquinone, decyl chloride And thioxanthones, and these can be used alone or in combination of two or more.

The heat-resistant photosensitive composition of the present invention contains a polyimide resin which is an addition reaction product of an epoxy compound having an imide group and a monobasic acid having a photopolymerizable unsaturated group, a sensitizer or a photoinitiator. A heat polymerization inhibitor, an inorganic filler, and a coloring agent can be added and blended within a range not contrary to the purpose of the above. As the thermal polymerization inhibitor used here, p-methoxyphenol, hydroquinone, 2,6
-Di-t-butyl-4-methylphenol, methyl ether hydroquinone, benzoate, benzoquinone,
-Hydroxymethyl-2,6-di-t-butylphenol and the like, and these can be used alone or in combination of two or more. Thermal polymerization inhibitor, heat-resistant photosensitive composition
It is desirable to add 0.05 to 2.0 parts by weight to 100 parts by weight. In addition, as an inorganic filler or coloring agent, silica,
Magnesium carbonate, calcium carbonate, sodium sulfate,
Examples thereof include talc, bentonite, and phthalocyanine green, and these can be used alone or in combination of two or more.

The heat-resistant photosensitive composition of the present invention is soluble in an organic solvent and, when used as a material for forming an insulating protective film or the like, is dissolved in an organic solvent at a ratio of 5 to 40% by weight, preferably 15 to 30% by weight. It can be used as a resin liquid. As the organic solvent used here, N, N-dimethylsulfoxide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2 -Pyrrolidone, diglyme, hexamethylenephosphamide, γ-butyllactone, cyclohexanone, etc., and these can be used alone or in combination of two or more.

An insulating protective film can be formed using the photosensitive resin solution thus prepared. That is, a photosensitive resin liquid is applied to a substrate and dried to remove an organic solvent. The application to the substrate can be performed, for example, by a method such as spraying, dipping, spin coating, roll coating, curtain coating and the like. The coating film is dried by hot air drying, far infrared drying, etc.
The reaction is performed at a temperature of 100 ° C. or less, preferably 60 ° C. or less. After drying, a negative photomask is placed on the coating film, and ultraviolet rays are irradiated using, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, or the like. Next, this is developed by a method such as spraying a developing solvent or dipping in a developing solvent to wash off the unexposed portion. As a developing solvent, in addition to the organic solvent used for preparing the photosensitive resin liquid,
An organic solvent such as isoamyl acetate or a mixed solvent system of these with cyclohexanone can be used. Development is 15
It is desirable to perform the treatment while applying ultrasonic waves at a temperature of ~ 35 ° C. Next, heat treatment is performed at 120 to 180 ° C. for 10 to 60 minutes to form an insulating protective film having openings. Wiring can be provided on this insulating protective film and used as an intermediate insulating layer, or can be used as a passivation layer without providing wiring.

(Action) The heat-resistant photosensitive composition of the present invention has a polyimide having a polyimide resin obtained by an addition reaction of a specific epoxy resin having an imide group and a monobasic acid having a photopolymerizable unsaturated group. A composition exhibiting sufficient heat resistance and photosensitivity and having good storage stability can be obtained.

(Examples) Next, the present invention will be described specifically with reference to examples. In the following examples, “parts” means “parts by weight”.

Example 1 After replacing the inside of a three-neck flask with dry nitrogen through a flask, 27.50 parts of an epoxy compound having an imide group derived from benzophenonetetracarboxylic anhydride, 9.55 parts of cinnamate, and 0.03 part of triethylamine were added, and the mixture was heated to 150 ° C. Heat, then raise to 200 ℃ at a heating rate of 20 ℃ / 1 hour,
The reaction was stirred for 4 hours at 200 ° C. while suppressing the heat generated by the reaction. After the completion of the reaction, diglyme was charged into the flask and cooled. The reaction solution was poured into a mixed solution of methanol and water to precipitate a polyimide resin. The precipitated polyimide resin is dried to obtain a brown polyimide resin powder.
36.80 g were obtained. 20 g of this polyimide resin powder was dissolved in 80 parts of diglyme, and 2 parts of benzoin isopropyl ether was added and blended as a photopolymerization initiator to prepare a heat-resistant photosensitive composition (A).

Example 2 After replacing the inside of the flask with dry nitrogen in a three-necked flask, 27.50 parts of an epoxy compound having an imide group derived from pyromellitic acid, 5.72 parts of acrylic acid, and 0.03 part of triethylamine were added, and the mixture was heated to 150 ° C. 20 ℃ /
The temperature was raised to 200 ° C. at a heating rate of 1 hour, and the reaction was agitated for 4 hours at 200 ° C. while suppressing the heat generated by the reaction. After the completion of the reaction, diglyme was charged into the flask and cooled. The reaction solution was poured into a mixed solution of methanol and water to precipitate a polyimide resin. The precipitated polyimide resin was dried to obtain 32.40 g of brown polyimide resin powder. Dissolve 20 g of this polyimide resin powder in 80 parts of diglyme,
Benzoin isopropyl ether 2 as photopolymerization initiator
And heat-resistant photosensitive composition (B).

Example 3 After replacing the inside of a three-necked flask with dry nitrogen through nitrogen, 27.50 parts of an epoxy compound having an imide group derived from benzophenonetetracarboxylic anhydride, 6.63 parts of methacrylic acid and 0.03 part of triethylamine were added, and the mixture was heated to 150 ° C. After heating, the temperature was raised to 200 ° C. at a heating rate of 20 ° C. for 1 hour, and the reaction was stirred for 4 hours at 200 ° C. while suppressing the heat generated by the reaction. After completion of the reaction, diglyme was charged into the flask to cool. The reaction solution was poured into a mixed solution of methanol and water to precipitate a polyimide resin. The precipitated polyimide resin was dried to obtain 33.10 g of a brown polyimide resin powder. 20 parts of this polyimide resin powder was dissolved in 80 parts of diglyme, and 2 parts of benzoin isopropyl ether was added and blended as a photopolymerization initiator to prepare a heat-resistant photosensitive composition (C).

Heat-resistant photosensitive compositions (A) and (B) obtained in Examples 1 to 3.
And (C) were applied to a uniform thickness by spin coating on a silicon wafer. Next, the coating film was dried in a hot air dryer at 50 ° C. for 30 minutes. The coating thickness after drying was 4 μm. A negative photomask char was placed on the coating film, and irradiation was performed using a 250 W high-pressure mercury lamp. Next, the unexposed portion was washed away using cyclohexanone / isoamyl acetate as a developing solution. Furthermore, after rinsing with isoamyl acetate,
After drying, heat treatment was performed at 150 ° C. for 30 minutes in a thermostatic dryer to form an insulating protective film on the silicon wafer.

The heat-resistant photosensitive composition of the present invention was tested for storage stability, curability, heat resistance, adhesion, moisture resistance, and chemical resistance. The results are shown in Table 1, and all of the present inventions were excellent, and the effects were confirmed.

[Effects of the Invention] As is clear from the above description and the results in Table 1,
The heat-resistant photosensitive composition of the present invention has excellent heat resistance, photosensitivity, adhesion, chemical resistance, moisture resistance, and storage stability, and is suitable as an insulating protective layer or a passivation layer for solid-state devices. .

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03F 7/027 C08F 299/02 C08G 73/10

Claims (1)

(57) [Claims] (1) an epoxy compound having an imide group represented by the following general formula: (Where R is (B) A heat-resistant photosensitive composition comprising: a polyimide resin obtained by reacting a monobasic acid having a photopolymerizable unsaturated group; and a sensitizer or a photopolymerization initiator.