JPH0253779B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel 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 field of electronics industry, semiconductor circuits, hybrid circuits, and printed circuits have been moving toward multilayering due to the demand for higher densities. 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 a heat-resistant photoresist with practical characteristics could be obtained for the first time by introducing an acrylate group into an aromatic polyamic acid. , we have completed the present invention.

That is, the present invention provides a reaction product of an aromatic polyamic acid and (meth)acrylic acid chloride, a compound having an ethylenically unsaturated double bond, and a carbonyl compound, a peroxide, an azo compound, a sulfur compound, The present invention provides a heat-resistant photoresist composition characterized by comprising one or more photopolymerization initiators selected from halides.

Since most ordinary heat-resistant polymers are insoluble in organic solvents, it is impossible to introduce or coat acrylate groups, and most solubilized heat-resistant polymers have the disadvantage of reduced heat resistance. Furthermore, there is a problem with chemical resistance after drying. In the composition of the present invention which eliminates such drawbacks, after coating, drying, exposure, and development,
Heat treatment at ~300°C makes it possible to obtain a photoresist film with excellent insulation, chemical resistance, and heat resistance.

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 diphenyl sulfone, 1,4-di(P-aminophenoxy)benzene, 1,3-di(P-aminophenoxy)benzene, 4,4'-di(O-aminophenoxy) diphenyl sulfone, 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'-diaminophenylsulfide-3-carbonamide, 3,4'-diaminodiphenylsulfide-4-carbonamide, 3,3'-diaminodiphenylsulfide-4-carbonamide, 3, 4'-diaminodiphenyl sulfide-
Aromatic diaminoamide compounds such as 3'-carbonamide and 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'-sulfonyldiphthalic acid, 3,3',4,4'-diphenyl ether tetracarboxylic acid, trimellitic acid, diphenylmethane-3,3',4-tricarboxylic acid, diphenyl ethertetracarboxylic acid, enyl ether-3,3',4-tricarboxylic acid, diphenylsulfide-3,3',4-tricarboxylic acid, diphenylsulfone-3,3',4-
tricarboxylic acid, diphenylpropane-3,3',
Aromatic polyamic acids obtained from aromatic tetracarboxylic acids or tricarboxylic acids such as 4-tricarboxylic acid and diphenyl 3,3',4-tricarboxylic acid, or their anhydrides, lower alkyl esters, acid halides, etc. are suitable. .

In the reaction between the aromatic polyamic acid and (meth)acrylic acid chloride, (meth)acrylic acid chloride is used in an amount of 0.001 to 10 moles per mole of polymerized units of the aromatic polyamic acid.

The introduction rate of acrylate groups is preferably in the range of 0.1 to 100%, and the acrylate 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 to 24 hours at the following temperatures:

Aromatic polyamic acid solutions with acrylate 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 and removing impurities, it may be used by dissolving it again in a polar solvent such as dimethylacetamide.

Examples of compounds having an ethylenically unsaturated double bond used in the present invention include 2-ethylhexyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, polypropylene glycol mono(meth)acrylate, and ethylene glycol di(meth)acrylate. , butylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, (meth)acrylamide, N,N'-methylenebis(meth)acrylamide , hexamethylene bis(meth)acrylamide, etc. These compounds are added in an amount of 0.1 to 100% by weight based on the above polymer.
In particular, it is preferably used in a range of 0.5 to 50% by weight.

Photopolymerization initiators 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,
Azo compounds such as azobisisobutyronitrile,
Examples include sulfur compounds such as tetraethylthiuram disulfide, halogen compounds such as carbon tetrachloride, and these may be used alone or in combination. The amount of these photopolymerization initiators added is 0.01 to 20% by weight, especially 0.1 to 10% by weight based on the above polymer.
is the preferred range.

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. 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 photopolymerization of the acrylate groups. . 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. Next, heat treatment is performed at 200 to 300°C.

In the heat-resistant photoresist composition of the present invention, (meth)acrylic acid chloride bonds (reacts) with the terminal amino group or the amide group of the main chain of polyamic acid when irradiated with light, so that it is difficult to convert into polyimide by heating. Removes water with low molecular weight,
Furthermore, a photoresist is obtained in which intermolecular crosslinking is increased, the film thinning rate is small, film defects are less likely to occur, and at the same time 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 1.5 parts by weight of an aromatic polyamic acid synthesized from 4,4'-diaminodiphenyl ether and pyromellitic dianhydride was dissolved in 20 parts by weight of dimethylacetamide, and then 0.5 parts by weight of acrylic acid chloride and 1 part by weight of pyridine were dissolved. After reacting at 55°C for 9 hours, the mixture was poured into a mixed solvent of 125 parts by weight of methanol and 250 parts by weight of water to precipitate the aromatic polyamic acid into which acrylate groups had been introduced, and then washed with methanol. After drying, the product was obtained quantitatively. The introduction rate of acrylate groups in the obtained product was 5%.

0.2 parts by weight of the above aromatic polyamic acid into which acrylate groups have been introduced, 0.01 parts by weight of N,N'-methylenebisacrylamide, and 1,4-naphthoquinone
Dissolve 0.004 parts by weight in dimethylacetamide,
After coating and drying on a glass substrate to form a coating film with a thickness of 5 μm, a predetermined pattern was exposed for 5 minutes using a 3 kW mercury lamp. After that, after washing out the non-exposed areas using dimethylacetamide,
A negative uneven pattern was obtained by heat treatment at 300°C for 1 hour. As a result, the film reduction rate (calculated by measuring the thickness by optical phase difference method) due to heating of the pattern was 5%. In addition, when copper foil was treated in the same manner as above, there was no problem with insulation up to 1 kV. Furthermore, in a heat resistance test using a thermobalance, weight loss was measured at a heating rate of 10°C/min under a nitrogen stream, and no significant weight loss was observed up to 450°C.

Comparative example Pyromellitic acid and allyl alcohol were reacted and then converted to acid chloride.
The aromatic polyamic acid obtained by reacting with 4,4'-diaminophenyl ether was blended and evaluated in the same manner as in Example 1. As a result, the film thinning rate was 25%, and the insulation was defective at 1kV.

Claims (1)

[Claims] 1. Reaction products of aromatic polyamic acid and (meth)acrylic acid chloride, compounds having ethylenically unsaturated double bonds, and carbonyl compounds, peroxides, azo compounds, sulfur compounds, and halides. A heat-resistant photoresist composition comprising one or more selected photopolymerization initiators.