JPH0145051B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel highly sensitive photoresist composition having excellent insulation properties, chemical resistance and heat resistance.

Various photoresists have been developed so far, but most of them are only photosensitive;
There is no material that combines properties such as photosensitivity, insulation, chemical resistance, and heat resistance.

In recent years, in the electronics industry, semiconductor circuits, hybrid circuits, printed circuits, etc.
Due to the demand for higher density, the trend is towards multi-layering. However, with conventional photoresists,
It has poor properties such as insulation, chemical resistance, and heat resistance, and it is impossible to leave it in the above circuit.
There is a need for a photoresist that has excellent insulation, chemical resistance, and heat resistance and can remain in the above circuit.

As a result of intensive research to develop a photoresist with the above characteristics, the present inventors discovered that by introducing a cinnamate group into an aromatic polyamic acid,
It was discovered that a heat-resistant photoresist with high sensitivity and practical characteristics could be obtained for the first time, and the present invention was completed.

That is, the present invention provides a reaction product of an aromatic polyamic acid and cinnamic acid chloride, an aromatic hydrocarbon, an aromatic amino compound, an aromatic nitro compound,
The present invention provides a heat-resistant photoresist composition characterized by comprising one or more sensitizers selected from phenolic compounds, aromatic ketones, quinones, and anthrones.

Since most ordinary heat-resistant polymers are insoluble in organic solvents, introduction and coating of cinnamate groups is impossible, and most solubilized heat-resistant polymers have the disadvantage of reduced heat resistance. Furthermore, there is a problem with chemical resistance after drying. The composition of the present invention, which eliminates these drawbacks, has high sensitivity and is easy to apply, dry, expose, and
After development, heat treatment at 200 to 300°C makes it possible to obtain a photoresist film with excellent insulation, chemical resistance, and heat resistance.

The aromatic polyamic acids used in the present invention include 4,4'-diaminodiphenyl ether, 4,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, metaphenylenediamine, paraphenylenediamine, 4,4'-diaminodiphenylpropane, 4, 4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,6-diaminopyridine,
4,4'-di(P-aminobenzoin) diphenyl ether, 4,4'-di(P-aminophenoxy)
Aromatic diamines such as diphenylsulfone, 1,4-di(P-aminophenoxy)benzene, 1,3-di(P-aminophenoxy)benzene, 4,4′-di(O-aminophenoxy)diphenylsulfone, or 4,4'-diaminodiphenyl ether-3-sulfonamide, 3,4'-diaminodiphenyl ether-4-sulfonamide, 3,4'-diaminodiphenyl ether-3'-sulfonamide, 3,3' -Diaminodiphenyl ether-4-
Sulfonamide, 4,4'-diaminodiphenylmethane-3-sulfonamide, 3,4'-diaminodiphenylmethane-4-sulfonamide, 3,4'-
Diaminodiphenylmethane-3'-sulfonamide, 3,3'-diaminodiphenylmethane-4-sulfonamide, 4,4'-diaminodiphenylsulfone-3-sulfonamide, 3,4'-diaminodiphenylsulfone -4-sulfonamide, 3,
4'-diaminodiphenylsulfone-3'-sulfonamide, 3,3'-diaminodiphenylsulfone-
4-sulfonamide, 4,4'-diaminodiphenylsulfide-3-sulfonamide, 3,4'-
Diaminodiphenylsulfide-4-sulfonamide, 3,3'-diaminodiphenylsulfide-4-sulfonamide, 3,4'-diaminodiphenylsulfide-3'-sulfonamide, 1,
4-diaminobenzene-2-sulfonamide,
4,4'-diaminodiphenyl ether-3-carbonamide, 3,4'-diaminodiphenyl ether-4-carbonamide, 3,4'-diaminodiphenyl ether-3'-carbonamide, 3,3' ―
Diaminodiphenyl ether-4-carbonamide, 4,4'-diaminodiphenylmethane-3-carbonamide, 3,4'-diaminodiphenylmethane-4-carbonamide, 3,4'-diaminodiphenylmethane- 3'-carbonamide, 3,3'-diaminodiphenylmethane-4-carbonamide,
4,4'-diaminodiphenylsulfone-3-carbonamide, 3,4'-diaminodiphenylsulfone-4-carbonamide, 3,4'-diaminodiphenylsulfone-3'-carbonamide, 3,3' ―
Diaminodiphenylsulfone-4-carbonamide, 4,4'-diaminodiphenylsulfide-
3-Carbonamide, 3,4'-diaminodiphenylsulfide-4-carbonamide, 3,3'-
Aromatic diamino compounds such as diaminodiphenylsulfide-4-carbonamide, 3,4'-diaminodiphenylsulfide-3'-carbonamide, 1,4'-diaminobenzene-2-carbonamide, and 3, 3',4,4'-benzophenonetetracarboxylic acid, pyromellitic acid, 3,3',4,
4′-diphenyltetracarboxylic acid, 2,3′,6,
7'-naphthalenetetracarboxylic acid, 1,4,5,
8-naphthalenetetracarboxylic acid, 3,4,9,
10-perylenetetracarboxylic acid, 4,4'-sulfonyl diphthalic acid, 3,3',4,4'-diphenyl ether tetracarboxylic acid, trimellitic acid, diphenylmethane-3,3',4-tricarboxylic acid, diphenyl ether tetracarboxylic acid, diphenylmethane-3,3',4-tricarboxylic acid, enyl ether-3,3',4-tricarboxylic acid, diphenylsulfide-3,3',4-tricarboxylic acid, diphenylsulfone-3,3',4-
Tricarboxylic acid, diphenylpropane-3,3',
4-tricarboxylic acid, diphenyl-3,3',4-
Aromatic polyamic acids obtained from aromatic tetracarboxylic acids such as tricarboxylic acid or tricarboxylic acids or their anhydrides, lower alkyl esters, acid halides, etc. are suitable.

In the reaction between the aromatic polyamic acid and cinnamic acid chloride, 0.001 to 10 moles of cinnamic acid chloride are used per mole of polymerized units of the aromatic polyamic acid.

The introduction rate of cinnamate groups is preferably in the range of 0.1 to 100%, and the cinnamate groups may be introduced only at the ends. Further, it is preferable to use a quaternary ammonium salt, a tertiary amine, or the like as a catalyst in the above reaction.

The reaction is carried out in an organic polar solvent such as N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, hexamethylphosphoamide, benzene, toluene, xylene, dioxane, cresol, etc. It is possible to coexist with a normal solvent of 150℃
It is carried out for 1-24 hours at the following temperatures:

Aromatic polyamic acid solutions with cinnamate groups introduced can be used as they are for certain specific purposes, but they can be separated by precipitation in a solvent that does not dissolve the polymer, such as water, methanol, acetone, toluene, or cyclohexane. After obtaining it and removing impurities, it may be used by dissolving it again in a polar solvent such as dimethylacetamide.

Although the above-mentioned aromatic polyamic acid into which a cinnamate group has been introduced has photosensitivity even when used alone, it is practically preferable to add a sensitizer to it in order to increase the sensitivity. Addition amount is 0.01 to polymer
A preferred range is 50% by weight, especially 0.1 to 10% by weight.

Sensitizers used in the present invention include aromatic hydrocarbons such as naphthalene, anthracene, phenanthrene, and chrysene; nitrobenzene, P-dinitrobenzene, 1,3,5-trinitrobenzene, P-nitrodiphenyl, and m-nitroaniline. , P-nitroaniline, 2,4-dinitroaniline, picramide, 2-chloro-4-nitroaniline, 2,6-dichloro-4-nitroaniline,
Aromatic amino compounds, aromatic nitro compounds, phenolic compounds such as P-nitrophenol, 2,4-dinitrophenol, 2,4,6-trinitrophenol; benzaldehyde, 9-anthraaldehyde, acetophenone, benzophenone, dibenes Aromatic ketones such as zalacetone, benzyl, P,P'-diaminobenzophenone, P,P'-dimethylaminobenzophenone, P,P'-tetramethyldiaminobenzophenone; 1,2-
Quinones such as naphthoquinone, 1,4-naphthoquinone, anthraquinone, 1,2-benzanthraquinone; anthrone, 1,9-benzanthrone, 6-phenyl-1,9-benzanthrone,
There are anthrones such as 2-keto-3-aza-1,9-benzanthrone and 3-methyl-1,3-diaza-1,9-benzanthrone, and these may be used alone or in combination. , a third component may also be added.

A suitable solvent such as the above-mentioned reaction solvent in which the present composition is substantially dissolved is used, and the viscosity of the solution can be adjusted according to the desired thickness of the coating. applied.

An example of the image forming process of the present invention is shown below.
The composition according to the invention is applied onto a substrate, dried to a substantially non-viscous state, and exposed in a predetermined pattern to ultraviolet light, e.g. from a mercury lamp, in order to cause photodimerization of the cinnamate groups. Ru. Exposure times are chosen accordingly, but longer exposure times are generally not harmful. After exposure to ultraviolet light or the like, the unexposed areas are washed out using a suitable solvent such as the reaction solvent, a mixed solvent of the reaction solvent and the precipitation solvent, or an aqueous alkaline solution. Then 200-300
Heat treatment at ℃.

In the heat-resistant photoresist composition of the present invention, when irradiated with light, cinnamic acid chloride bonds (reacts) with the terminal amino group or the amide group of the main chain of polyamic acid. A photoresist can be obtained in which small amounts of water are removed, intermolecular crosslinking is increased, the film thinning rate is small, film defects are less likely to occur, and film strength and heat resistance are improved.

In order to further clarify the aspects of the present invention, as follows:
Although the present invention will be explained by giving examples, the scope of the present invention is not limited by the examples.

Example 1 Synthesized from 4,4'-diaminodiphenyl ether-3-carbonamide, 4,4'-diaminodiphenyl ether and 3,3',4,4'-benzophenonetetracarboxylic dianhydride. After reacting 7 parts by weight of aromatic polyamic acid, 5 parts by weight of cinnamic acid chloride and 2 parts by weight of pyridine in 100 parts by weight of dimethylacetamide at 50°C for 4 hours,
The mixture was poured into a mixed solvent of 250 parts by weight of methanol and 500 parts by weight of water to precipitate the aromatic polyamic acid into which cinnamate groups had been introduced, followed by washing with methanol and drying to obtain a quantitative product. The introduction rate of cinnamate groups in the obtained product was 10%.

0.5 parts by weight of the above-mentioned aromatic polyamic acid into which a cinnamate group has been introduced and 0.01 parts by weight of P,P'-tetramethyldiaminobenzophenone are dissolved in dimethylacetamide, coated on a glass substrate and dried.
After forming a coating film of 5 μm, a predetermined pattern was exposed for 5 minutes using a 3 kW mercury lamp. Thereafter, the non-exposed areas were washed out using dimethylacetamide, and then heat treated at 300° C. for 1 hour to obtain a negative uneven pattern. The film thinning rate of this pattern (calculated by measuring the thickness using optical phase difference method), insulation properties (copper foil treated in the same manner as above), and heat resistance as determined by thermobalance (under nitrogen flow). Ten
As a result of measuring the weight loss (at a heating rate of ℃/min), the film reduction rate was 5%, and the insulation was satisfactory up to 1kV.
Regarding heat resistance, no significant weight loss was observed up to 500°C.

Comparative Example An aromatic polyamic acid obtained by reacting pyromellitic dianhydride with cinnamic acid alcohol and then converting it into acid chloride was reacted with 4,4'-diaminodiphenyl ether. As a result of the same blending treatment as in 1, the film reduction rate was 45%, and insulation failure occurred at 1kw.

Claims (1)

[Claims] 1. A reaction product of an aromatic polyamic acid obtained from an aromatic diamine or an aromatic diamino compound, an aromatic tetracarboxylic acid or tricarboxylic acid, or an anhydride thereof, a lower alkyl ester, or an acid halide, and a cinnamic acid chloride; 1 selected from aromatic hydrocarbons, aromatic amino compounds, aromatic ketones, quinones, and anthrones
A heat-resistant photoresist composition comprising at least one sensitizer.