JPS6023341B2 - Heat-resistant photoresist composition and method for producing the same - 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 there are no photoresists that combine properties 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 demands for higher density.

However, the conventional photoresist has poor properties such as insulation and heat resistance, and it is impossible to leave it in the above circuit. A photoresist is desired. The present inventors aimed to develop a photoresist with the above characteristics.As a result of intensive research, we were able to develop a heat-resistant photoresist with practical characteristics by introducing acrylate groups into polyamideimide soluble in organic polar solvents. The present inventors have discovered that the following can be obtained, and have completed the present invention.

That is, the present invention is based on the general formula {1} or,
〇2, CH2, C〇, C〇〇, C(CH3)2, and S, which may be the same or different.

), YI is H or Y, (Z is H or CH3), m is 0 or a positive integer, and n is a positive integer.

], a compound having an ethylenically unsaturated double bond, and an amazing photopolymerization initiator selected from carbonyl compounds, peroxides, azo compounds, sulfur compounds, and halides. A heat-resistant photoresist composition characterized by comprising the following formula:

,S〇2,CH2,C〇,C〇〇,C(CH3)2,S
and these may be the same or different from each other. ), m is 0 or a positive integer, and n is a positive integer. ] A method for producing a heat-resistant photoresist, which comprises reacting a polyamideimide soluble in an organic polar solvent represented by the following formula with (meth)acrylic acid chloride or glycidyl (meth)acrylate in an organic polar solvent. This is what we provide. Ordinary polyamideimide is not susceptible to organic polar solvents, so it is impossible to introduce acrylate groups or coat it. Although it is possible to introduce an acrylate group,
It is difficult to control the reaction, and because polyamic acid has carboxyl groups adjacent to amide bonds, it is easily hydrolyzed, and if stored as a solution for a long time, it will become heavy due to hydrolysis. It has the disadvantage that the molecular weight of the coalesce is significantly reduced, and furthermore, a high temperature treatment is required after coating to convert the polyamic acid to polyamidimide.

In the present invention, which eliminates these drawbacks, acrylate groups can be easily introduced by using polyamideimide that is soluble in organic polar solvents, and the resulting photoresist is stable and coatable. , it becomes possible to obtain a photoresist film with good thermal stability and electrical properties simply by removing the solvent. The general formula of the present invention, or
〇2, CH2, C〇. C〇〇,CCH3)2,S are shown, and these may be the same or different from each other.

) and Y. Y represents H or Y, (Z represents H or CH3), m represents 0 or a positive integer, and n represents a positive integer.

] The polymer represented by the following general formula or, Or [Here A.J. AJ' is (R represents hydrogen, an alkyl group, or a halogen, and X represents.

, S〇2, CH2, C〇. C〇〇,C(CH3)2,S
and these may be the same or different from each other. ), m is 0 or a positive integer, and n is a positive integer. It can be obtained by reacting a polyamideimide soluble in an organic polar solvent represented by the following formula with (meth)acrylic acid chloride or glycidyl (meth)acrylate. Polyamideimide soluble in the above organic polar solvent and (meth)acrylic acid chloride or glycidyl (meth)
In the reaction with acrylate, 0.001 to 10 moles of (meth)acrylic acid chloride or glycidyl (meth)acrylate are used per mole of polymerized units of polyamideimide.

The introduction rate of acrylate groups is 0.1 to 100%, that is, m/n = 0 to 1000, particularly m/n = 0 to 1.
00 is a preferred range.

Furthermore, an acrylate group may be introduced at the end. 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 also possible to coexist with ordinary solvents such as
It is carried out for 1 to 24 hours at a temperature below 15,000 ℃.

Further, in the above reaction, a tertiary amine or a quaternary ammonium salt may be used as a catalyst. A polyamideimide solution with acrylate groups introduced can be used as it is for certain specific purposes, but it can be used in water, methanol,
It is preferable to precipitate a polymer such as acetone, toluene, or cyclohexane in a solvent without a solvent, separate it, remove impurities, and then dissolve it again in a polar solvent such as dimethylacetamide for use.

The above general formula or
〇2, CH2, C〇, C〇〇, C(CH3)2, and S, which may be the same or different.

), m is 0 or a positive integer, and n is a positive integer. ] As a method for producing polyamideimide soluble in organic polar solvents represented by the general formula (where R represents hydrogen, an alkyl group, or a halogen, and X represents ○, S02, C, C○
, COO, C(CH3)2,S, which may be the same or different.

) A method of reacting aromatic diamine with trimellitic acid chloride represented by the general formula (where R represents hydrogen, alkyl group, or halogen, and ,S
and these may be the same or different from each other.

) A method of reacting bisimidocarboxylic acid represented by 3,3-diisocyanatodiphenyl, general formula ○=
C=N-Ar [or Ar')-N=C ○ [Here A[
is A stop' is (R represents hydrogen, alkyl group, halogen, X is 〇, S
〇2, CH2, C〇, C〇〇, C(CH3)2, and S, which may be the same or different.

) is shown. ] There is a method of reacting a diisocyanate represented by the formula with a bisimide carboxylic acid of the formula.

Examples of the compound 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, 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, Examples include hexamethylene bis(meth)acrylamide. These compounds have 0
．． It is preferably used in a range of 1 to 10% by weight, particularly 0.5 to 50% by weight. Photopolymerization initiators used in the present invention include acetophenone, diacetyl, benzophenone, benzoin, and benzoin isof.

Carbonyl compounds such as lopylether, chloroanthraquinone, naphthoquinone, peroxides such as penzoyl peroxide, azo compounds such as azobisisobutyronitrile,
Examples include 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 in the range of 0.01 to 2% by weight, particularly 0.1 to 1% by weight, based on the polymer. The composition can be prepared using a suitable solvent such as the above-mentioned reaction solvent in which the composition is substantially soluble, and the viscosity of the solution can be adjusted to suit the desired coating thickness. It is applied by etc.

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 photopolymerization of the acrylate groups. . The exposure time is chosen accordingly, but long 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 polymerization solvent, a mixed solvent of the polymerization solvent and the precipitation solvent, or an aqueous alkaline solution. Further, depending on the case, heat treatment may be performed after washing. In order to further clarify the aspects of the present invention, examples will be given and explained below.
The scope of the present invention is not limited by the examples.

Example 1 2.5 mm (0.023 mol) of m-phenylenediamine and 2.5 mm of pyridine were dissolved in 35 mm of dimethylacetamide under dry nitrogen, cooled to 5° C. with ice water, and trimellitic acid was dissolved. Anhydrous 4-monoyl chloride 4.3 (0
．． 020 mol) was added.

An exothermic reaction immediately occurred and the temperature of the solution rose to 35°C. After continuing to incubate for another hour at room temperature, a mixture of 10 parts of acetic anhydride and 4 parts of bijing was added, and 5 parts of
After heating for 2 hours, the mixture was poured into a mixed solvent of 250 parts methanol and 500 parts water to precipitate polyamidimide, which was then washed with methanol and dried. Polyamideimide 1 soluble in organic polar solvent thus obtained
．． 5% of dimethylacetamide was dissolved in 20% of dimethylacetamide, and then 0.81% of glycidyl methacrylate was added to give 55% of dimethylacetamide.
After reacting at ℃ for 5 hours, methanol 125' and water 2
The polyamideimide into which acrylate groups had been introduced was precipitated by pouring it into a mixed solvent with 50' and then washing with methanol and drying to obtain a quantitative product. The introduction rate of acrylate groups in the obtained product was 5%. 0.2 of the above polyamideimide into which acrylate groups have been introduced and 0.01 of tetramethylolmethanetetraacrylate
After dissolving 0.004 g of penzoin isopropyl ether in dimethylacetamide and applying the solution to a glass substrate and drying it, a predetermined pattern was illuminated for 5 minutes using a mercury lamp containing water.

Next, the non-exposed areas were washed out using a mixed solvent of dimethylacetamide and methanol (3:2 volume ratio) to obtain a negative uneven pattern. In a subsequent 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 400°C. Example 2 1.5 parts of the organic polar solvent-soluble polyamideimide obtained in Example 1 was dissolved in 20 parts of dimethylacetamide,
Next, 0.52 parts of acrylic acid chloride and 1 part of pyridine were added and reacted at 55 parts for 9 hours, and then poured into a mixed solvent of 12 parts of methanol and 25 parts of water to form a polyamideimide with acrylate groups introduced. was precipitated, then washed with methanol and dried to obtain a quantitative product.

The introduction rate of acrylate groups in the obtained product was 10%. 0.2 parts of the polyamideimide into which acrylate groups have been introduced, 0.01 parts of trimethylolpropane triacrylate, and 0.004 parts of 1,4 naphthoquinone are dissolved in dimethylacetamide, coated on a glass substrate, dried, and then A predetermined pattern was exposed for 5 minutes using a W mercury lamp. Next, the non-phosphorescent areas were washed out using a mixed solvent of dimethylacetamide and methanol (3:2 volume ratio) to obtain a negative uneven pattern. In the subsequent heat resistance test using a thermobalance, 10 qo/
When the weight loss was measured at a temperature increase rate of 1.5 min, no significant weight loss was observed up to 400°C. Note that the same results were obtained when polyamideimide soluble in organic polar solvents other than those in the above examples were used.

Claims (1)

[Claims] 1. 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 ▲ Mathematical formula , chemical formulas, tables, etc. ▼ Ar' has ▲ mathematical formulas, chemical formulas, tables, etc. ▼ (R represents hydrogen, alkyl group, halogen, X represents O,
SO_2, CH_2, CO, COO, C(CH_3)_
2 and S, which may be the same or different. ), Y_1 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Y is H or Y_1 (Z is H or CH_3),
m represents 0 or a positive integer, and n represents a positive integer. ]; a compound having an ethylenically unsaturated double bond; and one or more photopolymerization initiators selected from carbonyl compounds, peroxides, azo compounds, sulfur compounds, and halides. A heat-resistant photoresist composition characterized by: 2 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 ▲ Mathematical formulas, chemical formulas, tables, etc. There is a
There are chemical formulas, tables, etc. ▼ is O, SO_2, CH_2,
CO, COO, C(CH_3)_2, and S are shown, and these may be the same or different from each other. ), m is 0 or a positive integer, and n is a positive integer. ] Polyamideimide soluble in an organic polar solvent represented by (meth)acrylic acid chloride or glycidyl (
A method for producing a heat-resistant photoresist, which comprises reacting meth)acrylate in an organic polar solvent. 2 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Or [Here, Ar is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Ar' is ▲ Mathematical formula, There are chemical formulas, tables, etc.▼ (R represents hydrogen, alkyl group, halogen, X represents O,
SO_2, CH_2, CO, COO, C(CH_3)_
2 and S, which may be the same or different. ), m is 0 or a positive integer, and n is a positive integer. ] Polyamideimide soluble in an organic polar solvent represented by (meth)acrylic acid chloride or glycidyl (
A method for producing a heat-resistant photoresist, which comprises reacting meth)acrylate in an organic polar solvent.