JP2895571B2 - Heat-resistant photosensitive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial application field) The present invention mainly comprises a polyimide oligomer having an imide group and a photopolymerizable functional group, and has heat resistance, photosensitivity, storage stability and the like. The present invention relates to a heat-resistant photosensitive composition having excellent heat resistance. 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) As a polymer material for forming an insulating layer or a passivation layer of a solid-state element in a semiconductor process, a material having high photosensitivity and high heat resistance is required. 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 necessarily 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 phenylenediacrylic acid, heat resistance and photosensitivity, also excellent in storage stability and the like, it is found that the object is achieved,
The present invention has been 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) phenylenediacrylic acid represented by the following chemical formula And a sensitizer or a photoinitiator.

 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) phenylenediacrylic acid to an addition reaction.

(A) The epoxy compound having an imide group is represented by the following general formula.

(Where R is (B) Phenylenediacrylic acid has the following chemical formula and has a photopolymerizable unsaturated group.

The polyimide resin used in the present invention is capable of reacting (a) an epoxy compound having an imide group and (b) phenylenediacrylic acid in an organic solvent at a temperature of 150 to 200 ° C. for 3 to 12 hours. Can be. 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 photoinitiator 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, thioxanthones and the like,
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 phenylenediacrylic acid, a sensitizer or a photoinitiator, but within a range not contrary to the object of the present invention. , And if necessary,
A thermal polymerization inhibitor, an inorganic filler, and a colorant can be added and blended.

As the thermal polymerization inhibitor used here, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4
-Methylphenol, methylether hydroquinone,
Benzoate, benzoquinone, 4-hydroxymethyl-
Examples thereof include 2,6-di-t-butylphenol, and these can be used alone or as a mixture of two or more. The thermal polymerization inhibitor is 0.0% based on 100 parts by weight of the heat-resistant photosensitive composition.
It is desirable to add and mix 5 to 2.0 parts by weight. Examples of the inorganic filler and colorant include silica, magnesium carbonate, calcium carbonate, sodium sulfate, talc, bentonite, and phthalocyanine green. 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-type photomask chart is placed on the coating film, and ultraviolet rays are irradiated using 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. Then,
Develop by a method such as spraying a developing solvent or dipping in a developing solvent, and wash away the unexposed portions. As the 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 of these and cyclohexanone can be used. The development is desirably performed at a temperature of 15 to 35 ° C. while applying ultrasonic waves. 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 uses a polyimide resin obtained by an addition reaction of a specific epoxy resin having an imide group and phenylenediacrylic acid having a photopolymerizable unsaturated group to obtain a polyimide. Thus, a composition having sufficient heat resistance and photosensitivity and excellent 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 the flask with dry nitrogen in a three-necked flask, 27.50 parts of an epoxy compound having an imide group derived from benzophenonetetracarboxylic anhydride, 6.97 parts of phenylenediacrylic acid, and 0.03 part of triethylamine were added, and 150 ° C. At 20 ° C / hour for 2 hours.
Raise the temperature to 00 ° C and keep the heat
The reaction was stirred at 0 ° C. for 4 hours. 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 34.0 g of brown polyimide resin powder. This polyimide resin powder 2
0 g was dissolved in 80 parts of diglyme, and 2 parts of benzoin isopropyl ether was added and blended as a photoinitiator to prepare a heat-resistant photosensitive composition (A).

Example 2 After replacing the inside of a three-neck flask with dry nitrogen through a flask, 23.93 parts of an epoxy compound having an imide group derived from pyromellitic acid, and 6.97 parts of phenylenediacrylic acid
After heating to 150 ° C., the temperature was raised to 200 ° C. at a heating rate of 20 ° C. for 1 hour, and the mixture was stirred and reacted at 200 ° C. for 4 hours while suppressing heat generation due to 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 is dried to obtain a brown polyimide resin powder.
29.83 g were obtained. 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 photoinitiator to prepare a heat-resistant photosensitive composition (B).
Was manufactured.

Example 3 After replacing the inside of a three-necked flask with dry nitrogen through the flask, 26.88 parts of an epoxy compound having an imide group derived from 4,4'-oxydiphthalic anhydride, 6.97 parts of phenylenediacrylic acid, and 0.03 part of triethylamine were added. After heating to 150 ° C, 200 ° C at a heating rate of 20 ° C / hour
Up to 200 ° C while suppressing the heat generated by the reaction
For 4 hours with stirring. 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. 33.0 g of a brown polyimide resin powder was obtained. 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 photoinitiator 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. .

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 5/00 C09D 5/00 C 179/08 179/08 D G03F 7/027 514 G03F 7/027 514 H01L 21/31 H05K 3 / 46 T 21/768 H01L 21/90 S H05K 3/46 21/94 Z (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 299/00-299/08 C08F 290/00-290 / 14 C08G 73/00-73/26 C08G 59/00-59/72 C09D 1/00-201/10 G03F 7/00-7/42 H05K 3/00-3/46 H01L 21/00-21/98

Claims (1)

(57) [Claims] (1) an epoxy compound having an imide group represented by the following general formula: (Where R is (B) phenylenediacrylic acid represented by the following chemical formula And a sensitizer or a photopolymerization initiator.