JPS63297424A - Polyamide compound - Google Patents

Abstract

PURPOSE:To provide the titled compound having the structure obtained by introducing a side chain alkenyl group into an aromatic polyamide, applicable by coating to give a cured polyamide film having excellent heat-resistance and low thermal expansion coefficient and useful as a material for interlaminar insulation film of LSI, etc. CONSTITUTION:The objective compound contains the recurring unit of formula I (n is integer of 0-20; two phenylene groups are bonded with each other through m- or p-position). The compound can be produced e.g. by the polycondensation of a diamine of formula II (e.g. N,N'-diallyl-p- phenylenediamine) and a dicarboxylic acid dichloride of formula III (e.g. terephthaloyl dichloride).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polyamide compound that has excellent heat resistance and a low coefficient of linear expansion. More specifically, electrical and electronic component materials such as insulating materials and molding materials, especially surface coating materials for semiconductors, and LSI
An object of the present invention is to provide polyamide compounds as interlayer insulating films, heat-resistant substrate materials, etc.

[Conventional technology]

Conventionally, polyimide has been known as a surface coating material for semiconductors and an interlayer insulating film for LSI. This is a semiconductor, LSI
This is because high-temperature heat treatment is required in the manufacturing process, and polyimide has extremely excellent properties in terms of heat resistance.

However, in a multilayer wiring structure consisting of polyimide as an interlayer insulating film and an inorganic film such as SiN as a passivation film on a silicon substrate, the coefficient of thermal expansion of polyimide is larger than that of the inorganic material layer, and the coefficient of thermal expansion of polyimide is larger than that of the inorganic material layer. It has the disadvantage that peeling, warping, cracking, etc. occur due to thermal stress generated due to the difference in thermal expansion coefficients. Therefore, in order to form multilayer wiring, it is necessary to develop a low thermal expansion interlayer insulating film that has a coefficient of thermal expansion that matches the wiring materials such as copper and inorganic materials such as semiconductor p-8iN and p-810. It is essential.

Currently, fully aromatic polyamide is known as a material with excellent heat resistance and low thermal expansion. Polyparaphenylenetere-7-talamide, whose aromatic cyclic group is represented by a paraphenylene group, has a rigid molecular chain, so its coefficient of thermal expansion is small and exhibits a negative coefficient of thermal expansion even at high temperatures.

[Problem that the invention seeks to solve]

However, since the above-mentioned materials have high mutual affinity between molecules, they have low solubility and are completely insoluble in organic solvents, making it difficult to coat them onto a substrate by a method such as a spin cord.

An object of the present invention is to solve the above-mentioned drawbacks and to provide a polyamide compound that has excellent heat resistance, has a low coefficient of thermal expansion, and can be coated.

[Means for solving problems]

To summarize the present invention, the first invention of the present invention relates to a polyamide compound having the following general formula (1): (where n is an integer in the range of O≦n≦20, and two phenylene The second invention of the present invention is an invention relating to another polyamide compound, which is characterized by containing a repeating unit represented by (the group is bonded at the meta or para position). It is characterized by being a curing reactant of the polyamide compound of the first invention.

The present inventors synthesized various polyamides with different chemical structures of side chains and evaluated their properties. As a result, when an alkenyl group is introduced into an aromatic polyamide, it dissolves in an organic solvent, and when the side chain alkenyl group is cross-linked by heating or other treatment after coating on a substrate, it is possible to achieve the desired low thermal expansion and heat resistance. We have discovered that an insulating film that satisfies both requirements can be obtained.

The polyamide represented by the repeating unit (1) in the present invention can be prepared by polycondensation reaction of dicarboxylic acid dichloride and diamine according to the following reaction formula (where n is in the range of O≦n≦20). (integer, and the two unicine groups are bonded to the meta or para position) Alternatively, it can be produced by subjecting polyamide to an N-substitution reaction with an alkenyl halide according to the reaction formula below.

(However, n is an integer in the range of 0≦n≦20, X is a 10-gen group selected from chlorine, bromine, or iodine), and the two 72-2lene groups are bonded to the meta or para position. ) Here, n is preferably 0 to 20.

However, when n is 21 or more, the concentration of the rigid portion of the main chain in the matrix decreases and the degree of bending of the side chain increases, so that favorable low thermal expansion properties are imparted even after the polymerization reaction. I don't like it because I can't expect that.

In the present invention, the repeating unit (1) with a small n
Polyamide represented by and the repeating unit with large n (
It is also possible to use it by mixing it with the polyamide represented by 1), and by varying the mixing ratio, it is possible to arbitrarily control the coefficient of thermal expansion.

In the present invention, the curing reaction of the fluorenyl group of the polyamide represented by the repeating unit (1) can be carried out by simply heat-treating at 150°C or higher, or by using dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2.5-di - t-Butylperoxyhexene-5, lauroyl peroxide, t-butyl hyponitrite, azobisisobutyronitrile, azobiscyclohexanecarbonitrile, etc. method using an organic degenerate crosslinking agent, sulfur chloride, dithio According to the addition reaction method using adipine, pentamethylene diol, dinitroso, dinitrile oxide, etc., and the crosslinking method using sulfur, crosslinking can be carried out at a temperature of 150° C. or lower.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The invention is not limited to these examples.

Example 1 Sodium hydride t 1 (60% in paraffin) f was added to 750 ml of dimethyl sulfoxide, and 80 ml of dimethyl sulfoxide was added.
℃ for 1 hour to dissolve, cooled to 501℃, added 5ft of polyparaphelene lentilophthalamide powder to the above solution, stirred for 4 hours, then added allyl bromide t for 5 days. After reacting at 30°C for 8 hours, water was added to stop the reaction and precipitate the polymer. Filter this and wash thoroughly with water and Inglobil alcohol. After washing, drying at 60° C. under reduced pressure yielded a powdery polymer. The polyparaphenylene terephthalamide becomes soluble in solvents such as 2-chloroethylene, 1,2-dichloroethane, etc., and unreacted substances are removed through a filter with a pore size of 5βm.
It was purified by reprecipitation with acetone.

This poly! Pour the 1,2-dichloroethane solution of - into a glass, dry it at 50°C for 24 hours, remove the solvent, and then heat it at 250°C for 4 hours to obtain a tough film.Results of measuring the infrared absorption spectrum of this film ,2
It was confirmed that it was polyN-allylparaphenylene terephthalamide because it showed absorption of 950-5 G 90 an-'' K -CHl- and the absorption of 1540 crn''''1 disappeared.

Further, the heat resistance of this film was measured by thermogravimetric analysis (T()A-!10 manufactured by Shimadzu Rakusho Co., Ltd.), and as a result, the thermal decomposition temperature in air was 420°C. Furthermore, the linear expansion coefficient of this film was measured using a minute constant load thermal expansion coefficient needle (Shinku Rikosha TM-70).
As a result of measurement with 00), 2
I failed.

Example 2 A polyamide film was produced under the same conditions as in Example 1, using 4-bromo-1-butene (A7F) instead of allyl bromide. The thermal decomposition temperature of this film was 410° C., and the linear expansion coefficient was A3×10 −6 (° C.).

Example 3 Pour allyl bromide into the reacted bolimar in Example 1,
After drying at 50°C for 24 hours to remove the solvent, drying at 130°C,
The thermal decomposition temperature of this film, which was heat-treated in a nitrogen atmosphere for 4 hours, was 420°C, and the linear expansion coefficient was zxlo-a (°C-ri).
1), terephthal dichloride (4,060f), 20 meshes of magnesium powder (a, 12t), and dried tetrachloroethane (120-) were mixed and refluxed in a nitrogen stream for 7 hours. The evolution of hydrogen chloride was almost complete within the first 2 hours, and the viscosity of the solution gradually increased. Pore diameter 5μ
After removing unreacted substances through a filter, the product was purified by reprecipitation with acetone. Next, a film was prepared in the same manner as in Example 1, and the infrared absorption spectrum was measured.
It was confirmed that it was poly-N-allylparaphenylene terephthalamide because it showed -○H,- absorption at 2950 to 5090 cm-1 and the -NH- absorption at 1540 cM-' disappeared. In addition, the thermal decomposition temperature of this film in air is 420°C and the coefficient of linear expansion is 2 x 10
It was ``''・(tl knee).

〔Effect of the invention〕

As is clear from the above results, when an alkenyl group is introduced into an aromatic polyamide, it dissolves in an organic solvent, and when the side chain alkenyl group is polymerized by treatment such as heating after coating on a substrate, a semiconductor substrate A polyamide film with a low coefficient of thermal expansion comparable to that of the material and excellent heat resistance can be produced. Therefore, by using the polyamide compound according to the present invention, it is possible to provide surface covering materials for semiconductors and interlayer insulating films for LSIs that are free from cracks and have excellent high-temperature properties.

Claims (1)

[Claims] 1. The following general formula (1): ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) (However, n is an integer in the range of 0≦n≦20, and two A polyamide compound characterized in that it contains a repeating unit represented by the following (phenylene group is bonded at meta-position or para-position). 2. The following general formula (1): ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) (However, n is an integer in the range of 0≦n≦20, and the two phenylene groups are in the meta position or A polyamide compound characterized in that it is a curing reactant of a polyamide compound containing a repeating unit represented by ) bonded at the para position.