JPS5950049B2 - Heat-resistant photoresist composition - Google Patents

Description

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

Various photoresists have been developed so far, but most of them are only photosensitive, and none have characteristics such as photosensitivity, insulation, and heat resistance. In recent years, in the field of electronic industry, semiconductor circuits, hybrid circuits, printed circuits, and the like have been moving toward multilayering due to the demand for higher density.

However, conventional photoresists have poor properties such as insulation and heat resistance, and cannot be left in the above circuits.However, photoresists with excellent insulation and heat resistance that can be left in the above circuits is desired. As a result of intensive research to develop a photoresist with the above characteristics, the present inventors discovered a compound containing at least two ethylenically unsaturated double bonds in the molecule of polyamideimide that is soluble in organic polar solvents. The inventors have discovered that a heat-resistant photoresist with practical properties can be obtained for the first time by blending the above, and have completed the present invention.

That is, in the present invention, (R represents hydrogen, an alkyl group, or a halogen, and X is 0.
S02, CH2, CO, . COO. ．． C(CH3)2,
S, which may be the same or different.

), and n represents a positive integer. ] Polyamideimide soluble in organic polar solvents represented by z, compounds having at least two or more ethylenically unsaturated double bonds in the molecule, and carbonyl compounds, peroxides, azo compounds, sulfur compounds, and halides. The present invention provides a heat-resistant photoresist composition characterized by comprising one or more photopolymerization initiators selected from the following. Ordinary polyamideimide is insoluble in organic polar solvents, so
Polyamic acid, which cannot be coated and is soluble in organic polar solvents in the middle stages of polyamide-imide synthesis, is susceptible to hydrolysis due to the presence of carboxyl groups adjacent to amide bonds, resulting in If stored for a long period of time, the molecular weight of the polymer will drop significantly due to hydrolysis, and furthermore, high temperature treatment is required after coating to convert polyamic acid to polyamideimide. .

In the present invention, which eliminates these drawbacks, by using polyamideimide that is soluble in organic polar solvents, the resulting photoresist is stable and can be coated, and thermal stability and stability can be improved just by removing the solvent. It becomes possible to obtain a photoresist film with good electrical characteristics.

The general formula used in the present invention or [where Ar is Ar' (R represents hydrogen, an alkyl group, or a halogen;
O2, CH2, CO. COO. C(CH3)2 and S, which may be the same or different.

), and n represents a positive integer. ] The method for producing polyamideimide soluble in organic polar solvents is as follows:
In the general formula, R represents hydrogen, an alkyl group, or a halogen,
x is 0. S02, CH2, CO. COO. C (CH3)
2, S, which may be the same or different.

) A method of reacting an aromatic diamine represented by the general formula (where R represents hydrogen, an alkyl group, or a halogen;
S, which may be the same or different.

) represented by bis, imidocanolebonic acid and 3.3″-
A method of reacting diphenyl diisocyanate. General formula 0=C=N-Ar (or Ar')-N=C=0
r is Ar' (R is hydrogen, alkyl group, halogen, X is 0.S02, CH2
, C.O. COO. C(CH3)2 and S are shown, and these and P may be the same or different.

) and a method of reacting a bisimidecarboxylic acid of the formula.

Examples of compounds having at least two ethylenically unsaturated double bonds in the molecule used in the present invention include ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate. , trimethylolpropane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, N-N″-methylenebis(
Examples include meth)acrylamide and hexamethylene bis(meth)acrylamide. These compounds are preferably used in an amount of 1 to 200% by weight, particularly 5 to 100% by weight, based on the polymer. Examples of the photopolymerization initiator used in the present invention include carbonyl compounds such as acetophenone, diacetyl, benzophenone, benzoin, benzoin isopropyl ether, chloroanthraquinone, and naphthoquinone, peroxides such as benzoyl peroxide, azobisisobutyronitrile, etc. Examples include azo compounds such as , sulfur compounds such as tetraethylthiuram disulfide, halides such as carbon tetrachloride, and these may be used alone or in combination.

The amount of these photopolymerization initiators added is preferably from 0.01 to 20% by weight, particularly from 0.1 to 10% by weight, based on the polyamideimide. The composition is prepared using a suitable solvent such as N-N-dimethylacetamide, N-N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, hexamethylphosphoamide, etc., in which the composition is substantially soluble, and the viscosity of the solution is adjusted to the desired coating level. The solution can be adjusted according to the thickness of the coating, and the solution is applied by spraying, dipping, or using a roller.

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, for example from a mercury lamp.

Exposure times are chosen accordingly, but longer exposure times are generally not harmful. After exposure to ultraviolet rays or the like, the unexposed areas are washed out using a suitable solvent such as the coating solvent, a mixed solvent of the coating solvent and a non-solvent, or an alkaline aqueous solution. Further, depending on the case, heat treatment may be performed after washing. EXAMPLES In order to further clarify aspects of the present invention, examples will be given and explained below, but the scope of the present invention is not limited by the examples.

Example m - 2.5 g (0.023 mol) of phenylenediamine and 2 ml of pyridine were dissolved in 35 ml of dimethylacetamide under a stream of dry nitrogen, cooled to 5° C. with ice water, and the 4 monoacid of trimellitic anhydride was dissolved. Chloride 4.3g (0
．． 020 mol) was added.

An exothermic reaction immediately occurred and the temperature of the solution rose to 35°C. After stirring for another hour at room temperature, a mixture of 10 ml of acetic anhydride and 4 ml of pyridine was added, and after stirring at 50°C for 2 hours, a mixture of 250 ml of methanol and 500 ml of water was added.
1 to precipitate polyamideimide, which was then washed with methanol and dried. 0.2g of the polyamideimide thus obtained, 0.04g of tetranotyolmethanetetraacrylate, and 0.008g of benzoin isopropyl ether were dissolved in dimethylacetamide, coated on a glass substrate, dried, and then heated to 3K.
A predetermined pattern was exposed for 5 minutes using a W mercury lamp.

Claims (1)

[Claims] General formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, [Here, Ar is ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
Ar′ has ▲mathematical formula, chemical formula, table, etc.▼, ▲mathematical formula,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R represents hydrogen, alkyl group, halogen,
is O, SO_2, CH_2, CO, COO, C(CH_
3)_2 and S, which may be the same or different. ), and n represents a positive integer. ] A polyamideimide soluble in an organic polar solvent, a compound having at least two or more ethylenically unsaturated double bonds in the molecule, and a carbonyl compound, peroxide, azo compound,
A heat-resistant photoresist composition comprising one or more photopolymerization initiators selected from sulfur compounds and halides.