JPS6121130A - Photosensitive heat-resistant material - Google Patents

Abstract

PURPOSE:A material, containing a reaction product of a polyimide-isoindoloquinazolinedione precursor with an aziridine compound, having improved storage stability, and preparable in a simple production process. CONSTITUTION:A photosensitive heat-resistant material containing a reaction product obtained by reacting (A) a polyimide-isoindoloquinazolinedione precursor prepared by reacting an aromatic diamine expressed by the formula H2N-R1- NH2 (R1 is bifunctional organic group) with an aromatic diaminoamide expressed by formula I (R2 is trifunctional organic group) and an aromatic tetracarboxylic acid dianhydride expressed by formula II (R3 is tetrafunctional organic group) with (B) an aziridine compound expressed by formula III (R4 is a group having double bond capable of dimerizing or polymerizing with light or radiation). The component (B) in an amount of 0.2-2.0 equivalents based on carboxyl groups in the side chain of the component (A) is reacted therewith.

Description

[Detailed description of the invention] [Technical field of invention] The present invention relates to a novel photosensitive heat-resistant material.

[Prior art]

Conventionally, in the semiconductor industry, inorganic materials such as silicon oxide have been widely used as insulating layers and passivation layers of solid-state devices.

- Compared to inorganic materials, organic materials have properties such as low stress, excellent smoothness, and high purity. h. It has not been put to practical use in some semiconductor devices.

When using an organic material for the above-mentioned purpose, it is necessary to use a heat-resistant organic material because it involves a lot of heating work such as bonding. Therefore, polyimide, which usually has excellent heat resistance, has been widely studied.

When polyimide is used as an insulating layer or passivation layer of a solid-state device, photoresist is generally used in the process of decorating microfabrication such as conductive parts of upper and lower conductor layers and through holes for connection with external lead wires. Chemical etching treatment of polyimide is being carried out. That is, for example, after coating a substrate with polyamic acid, which is a polyimide precursor, and converting it into polyimide by heat treatment, a photoresist relief pattern is formed on the polyimide film, and the polyimide film is removed using a crack etching agent. A relief pattern is formed in the polyimide by selective chemical etching.

patterning of polyimide in the above process
i. Processes such as photoresist coating and peeling are required, making the entire process extremely complicated. Therefore, in order to simplify the microfabrication process, there was a high demand for the first heat-resistant material that could be patterned with direct light. As one of the above objects, Japanese Patent Publication No. 49-1+7374'8' proposed a photosensitive i-thermal material consisting of polyamic acid, dichromate, and acetate.

According to Nanane, it is possible to obtain a polyimide relief pattern by applying the above material to the entire substrate, drying it, exposing it to light using a normal optical method, developing it, and then heating it. However, this material has poor storage stability because it involves a dark reaction, and must be used immediately after being prepared as a photosensitive heat-resistant material by mixing dichromate. The cured product has disadvantages such as poor reliability as an insulating film.

In JP-A-49-115541, for example, the general formula (where R ke CHz=Ci(C!Hs)Coo(!H
A photosensitive heat-resistant material obtained by completely reacting a pyromellitic acid derivative shown in 20H2- and a diamine was proposed.

D) Since this pyromellitic acid derivative is a viscous liquid and is difficult to purify, the resulting resin is expensive.

Furthermore, JP-A-55-45746 describes that a photosensitive heat-resistant material can be obtained by completely reacting a polyamic acid with a monoepoxide having a photosensitive group such as glycidyl methacrylate. However, the reaction between epoxide and carboxylic acid is very complicated, requiring a reaction accelerator, and furthermore, there are drawbacks such as extremely poor storage stability after the reaction.

[Summary of the invention]

This invention was made in order to eliminate the drawbacks of the above-mentioned conventional products. An aromatic diaminoamide represented by the formula (in the formula, RsVi represents a trivalent organic group), and an aromatic tetracarboxylic acid represented by the general formula 0% (in the formula, R represents a tetravalent organic group) Polyimide-isoindoquinazolinedione 1111 precursor (A) vc, which is formed by reacting dianhydride with f4, and general formula (in the formula, Indicates a group having a double bond.

) By using an aziridine compound (obtained by Blk reaction), the purpose is to provide a novel photosensitive heat-resistant material with excellent storage stability and a simple manufacturing process. .

[Embodiments of the invention]

The aromatic diamine according to the present invention has a structure represented by the general formula (II, for example, P-)unishindiamine, 9m-phenylenediamine, 4.4'-diaminodiphenyl ether, 4.4'- Diaminodiphenylmethane, 4.4'-benzidine, 3.3'-benzidine, 4.4'-di(4-aminophenoxy)diphenylsulfone, 4.4'-di(3-aminophenoxy)diphenylsulfone and 1.5 - At least one type of diamino naphthalene is preferably used.

The aromatic diaminoamide according to this invention has the general formula (2
), examples include 2.5-diaminobenzoic acid amide, 2.4-diaminobenzoic acid amide, 4.4'-diaminodiphenyl ether-3-carboxylic acid amide, 4.4'- At least one of diaminodiphenylmethane-3-carboxylic acid amide and 4,4'-diaminodiphenylsulfone-3-carbo7 + (19 amide) is preferably used.

The aromatic tetracarboxylic dianhydride according to the present invention has a structure represented by the general formula (3), and includes, for example, pyromellitic dianhydride, 3.3',4.4'-benzophenonetetracarboxylic acid At least one of dianhydride and bisphthalic dianhydride is excellent as a final cured product! # It is a good play because it gives heat properties, but as long as it is aromatic σ), there is no harm in using any ρ).

In addition, when the above-mentioned aromatic diamine, aromatic diaminoamide and aromatic tetracarboxylic dianhydride are reacted to obtain a polyimide-isoindoloquinazolinedione precursor, it is inert to the above-mentioned reactants, [(Number of moles of diamine) + (Mole of diaminoamide ff): )/(Mole of aromatic tetracarboxylic dianhydride) = 1 It is preferable to carry out the reaction at a mixing ratio of .

As a solvent, for example, N,N'-dimethylacetamide,
N,N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoamide, and the like are preferably used.

Further, these reactions are preferably carried out at a temperature of 80° C. or lower for 2 to 10 hours. It becomes insoluble at temperatures above 80°C, and the reaction is insufficient at temperatures below 2 hours.

As the aziridine compound represented by the general formula (4) according to the present invention, at least one of, for example, H2 can be used.

Note that the reaction between the Konera aziridine compound and the imido-isoindoroquinazolinedione precursor is carried out under SO'CPT, preferably near room temperature, as insolubilization occurs at temperatures above 80"C. The photosensitive heat-resistant material of the present invention has extremely high storage stability because it progresses quickly without using a reaction accelerator such as a base and does not contain impurities. , 0.2 to 2.0% relative to the side chain carboxyl group in all of the above imido-isoindoquinazolinedione precursors of the aziridine compound.
It is preferable to react within a range of 0 equivalent, preferably 0.8 to 1.5 equivalent. If the amount is less than 0.2 equivalent, the crosslinking reaction upon exposure will not occur sufficiently, resulting in poor relief pattern forming ability. Moreover, if the amount exceeds 2.0 equivalents, the thermal stability of the cured product after heat treatment in the final step will be poor.

That is, the photosensitive heat-resistant material of the present invention has as its main component a compound obtained by reacting an imido-isoindoroquinazolinedione precursor with an aziridine compound. However, for example, when containing a photosensitizer in an amount of 0.01 to 1ON, a remarkable photosensitizing effect can be obtained.

Such photosensitizers include, for example, benzoin, benzoin ethyl ether, benzine methyl ether, benzoin isobutyl ether, anthraquinone, benzoquinone, β-methylanthraquinone, naphthoquinone, diphenyl sulfide, acetophenone.

At least one of benzophenone and 4,4'-tetramethyldiaminobenzophenone can be used.

The photosensitive heat-resistant material of this invention is spin-coated onto a silicon wafer, dried at 50 to 90°C, exposed to light through a predetermined pattern mask, and then N
-Methyl-2-pyrrolidone.

By developing with a solvent such as N,N-dimethylacetamide, the unexposed areas are washed away and a sharp relief pattern on the end surface is obtained. At temperatures below 50°C, viscosity remains due to insufficient volatilization of the solvent, and at temperatures above 90°C, insolubilization occurs. Furthermore, by subsequently performing heat treatment at 200 to 400°C, a cured product having excellent heat resistance, chemical resistance, and electrical properties and a good pattern can be obtained.

The photosensitive heat-resistant material of the present invention can be stably stored at room temperature and protected from light for several months.

The present invention will be explained in more detail below based on actual paddle examples, but the present invention is not limited to these examples.

Actual example 1 Into the fourth flask of SOOMA equipped with a thermometer, stirrer, nitrogen introduction tube, and calcium chloride tube, 8 g (0.04 mol) of 4,4'-diaminodiphenyl ether was added.
1.51 g (0.01 mol) of diaminobenzoic acid amide and 150 g of dried N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were added and dissolved. To this solution, 10.9 g (o, o 5 mol) of pyromellitic dianhydride was added at once, and the reaction was carried out at 20°C for 2 hours and at 80°C for 2 hours to prepare the imido-isoindoquinazolinedione. I got the body.

Furthermore, 2-(l-aziridinyl)ethyl meta 15.5
g (0,1 mo A heat-resistant material was obtained.

This was spin-coated onto a glass plate, dried at 80°C for 15 minutes, and then exposed to ultraviolet light for 30 seconds through a prescribed mask (ultra-high pressure mercury lamp 500W, 30cm).
.

After formation, a good relief pattern was obtained by dipping in NMP for 60-120 seconds.

Separately, the photosensitive heat-resistant material of the sister example of the present invention was applied to a copper plate, and the entire surface was exposed to light for 30 seconds using the same exposure device as above. Thereafter, it was heated at 200'C for 1 hour, at 300°C for 1 hour, and at 400°C for 30 minutes in a nitrogen atmosphere.

As a result of measuring the electrical properties of the cured product obtained by smelting, it was found that the dielectric strength voltage was 300 kV/mm, and the dielectric constant was 2.9 (1 kH2).
).

A volume resistivity of 4×10 15 Ω·am was obtained, and it was found that it exhibited electrical properties comparable to those of ordinary polyimide.

Furthermore, as a result of measuring the thermal weight loss under the condition of 5°C/min in air, it was found that the initial decomposition initiation temperature was 460°C, indicating excellent thermal stability.

Sister Examples 2 to 11 According to the self-content of each component shown in Table IK, the same operations as in Example 1 were carried out to obtain photosensitive heat-resistant materials of sister examples of the present invention.

The obtained material was applied to a glass plate and subjected to the same image forming process as in Example 1. The results are shown in Table 2. Apply, 100°C 30 minutes, 200°C1
After heat treatment at 350'C in a nitrogen stream for 1 hour, the electrical properties and heat resistance were measured. These results are also shown in Table 2.

According to the results, it can be seen that it exhibits electrical properties comparable to those of conventional polyimide, and also has excellent thermal stability.

In addition, after leaving it for 3 months at room temperature and shielded from light, the same image forming process as in Example 1 was performed to examine patterning properties.
The results are also shown in Table 2. According to the results, the storage period for conventional products that can be buttered is one month at room temperature and shielded from light, whereas it can be seen that the product has excellent storage stability.

The compounds used in Table 1 are abbreviated as follows.

Diamine PDS Diaminoamide Aromatic Tetracarboxylic Dianhydride Aziridine Compound H2 H2 [Effects of the Invention] As explained above, this invention has the following properties: aromatic diamine represented by the general formula 0% (2) (in which R2H represents a trivalent organic group); Polyimide-isoindoquinazolinedione precursor (A) V obtained by reacting the aromatic tetracarboxylic dianhydride represented by
Cl general formula (wherein R4 represents a group having a double bond that can be dimerized or polymerized by light or radiation) By using this material, it is possible to obtain a new photosensitive heat-resistant material that has excellent storage stability and a simple manufacturing process, and is useful as an insulating material that can be microfabricated by direct light, for example, for interlayer insulation of solid-state devices such as semiconductors. Materials, pansibase 7 materials F), insulating films for magnetic heads and thermal heads, and even solder resists for printed circuits.

It can also be applied to highly heat-resistant materials such as photoresists and lift-off materials.

Claims (6)

[Claims] (1) Aromatic diamine represented by the general formula H_2N-R_1-NH_2 (1) (in the formula, R_1 represents a divalent organic group), general formula ▲ mathematical formula, chemical formula, table, etc. There is an aromatic diaminoamide represented by ▼・・・・・・(2) (In the formula, R_2 represents a trivalent organic group) and a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼・・...(3) (In the formula, R_3 represents a tetravalent organic group.) A polyimide-isoindoquinazolinedione precursor (A ), there are general formulas ▲numerical formulas, chemical formulas, tables, etc.▼・・・・・・(4) (In the formula, R_4 represents a group having a double bond that can be dimerized or polymerized by light or radiation.) A photosensitive heat-resistant material containing a compound obtained by reacting an aziridine compound (B) represented by: (2) Claims containing 0.2 to 2.0 equivalents of the aziridine compound (B) reacted with the side chain carboxyl group of the polyimide-isoindoroquinazolinedione precursor (A) The photosensitive heat-resistant material according to item 1. (3) Divalent organic groups have ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
The photosensitive heat-resistant material according to claim 1 or 2 is one of the following: ▼ There are tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ . (4) Trivalent organic groups have ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
The photosensitive heat-resistant material according to claim 1 or 2, which is one of the following: ▼ Contains tables, etc. and ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼. (5) Tetravalent organic groups have ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
The photosensitive heat-resistant material according to claim 1 or 2, which is one of the following: ▼ Contains tables, etc. and ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼. (6) R_4 is H_2C=CHCOOCH_2CH_2
-, H_2C=(CH_3)COOCH_2CH_2-
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ The photosensitive heat-resistant material according to claim 1 or 2, which is one of the following.