JPS59145216A - Organic solvent-soluble photosensitive polyamide-imide - Google Patents

Abstract

PURPOSE:The titled photosensitive polyamide-imide excellent in heat resistance, electrical properties, and mechanical properties, prepared by polymerizing an aromatic tetracarboxylic acid with a specified aromatic diamine compound having a cinnamamide bond, and imidating the product. CONSTITUTION:An aromatic tetracarboxylic acid (dianhydride), e.g., 3,3',4,4'- biphenyltetracarboxylic acid, is polymerized with an aromatic diamine compound of the formula (e.g., 4,4'-diaminocinnamanilide) at about 100 deg.C or below for about 1-48hr in an organic solvent (e.g., N,N-dimethyl sulfoxide). The produced polyamide-imide precursor solution is diluted with an organic solvent and, after adding an imidating agent (acetic anhydride or pyridine), heated to about 100 deg.C or below for above 0.5-5hr to imidate the precursor into the purpose polyamide- imide.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel polyamideimide containing a photosensitive group,
Specifically, it has excellent heat resistance, electrical and mechanical properties, and is suitable as a material for forming insulating films and passivation films on solid-state devices in the semiconductor industry, and as an insulating material for semiconductor integrated circuits, multilayer printed wiring boards, etc. , relates to an organic solvent soluble photosensitive polyamideimide.

Insulating films and bars for solid-state devices in the semiconductor industry
- Materials for forming layer layers and interlayer insulating materials for semiconductor integrated circuits, multilayer printed wiring boards, etc. are required to have high resistance to 17J5 and high insulation properties. From this point of view, various proposals have been made to form the above-mentioned bancivation film etc. with polyimide, which has high heat resistance as well as insulation properties (Japanese Patent Laid-Open No. 4-1199).
9-115541, JP-A-54-116216, JP-A-54-116217, and JP-A-Sho 56
(Refer to Publication No.-45915, etc.).

However, among these, those using polyimide are generally solvent-infusible and do not have photosensitive groups, and in the above proposal, all polymers containing photosensitive groups are polyimide precursors. It is a modified form of carboxylic acid of polyamic acid such as amidation or esterification, and it is necessary to convert polyamic acid into polyimide during photocuring or post-baking after photocuring to form polyimide.

Furthermore, aromatic polyimides, which have excellent heat resistance, generally have poor solubility in solvents, and therefore are not suitable for forming relief patterns, which include a step of dissolving unexposed areas in an organic solvent after photocuring.

In addition, various photosensitive polyamide imides have been proposed as materials for forming insulating films and bashing films on solid-state devices in the semiconductor industry, and as interlayer insulating materials for semiconductor integrated circuits, multilayer printed wiring boards, and the like.

However, in many of these photosensitive polyamide-imides, trimellitic anhydride is used as the acid component, and after producing polyamide-imide by polycondensation with a diamine compound, the active hydrogen of the amide of the polyamide-imide is converted into a photosensitive group. (Japanese Patent Application Laid-Open No. 1989-89)
Since this substitution reaction is based on a polymer reaction, it is desirable to always introduce a predetermined amount of photosensitive groups into the polyamideimide.

Therefore, an attempt has been proposed to obtain a polyamide with a side chain containing an imide group by reacting materials containing photosensitive groups during polycondensation (see Japanese Patent Application Laid-Open No. 53-5298). The polyamide that is hydrogenated by this method has only amide bonds in its main chain and therefore does not have sufficient heat resistance.

In view of the above-mentioned current situation, the present inventors conducted various investigations with the aim of providing a photosensitive resin that can easily form a relief pattern with excellent heat resistance, electrical and mechanical properties, and found that aromatic An aromatic polyamideimide obtained from a tetracarboxylic acid or its dianhydride and a specific aromatic diamine compound having a cinnamamide bond is photosensitive and soluble in an organic solvent, and achieves the objective described in -F. I found out that I can get it.

17+1 The present invention was made based on the above findings, and involves polymerizing and imidizing an aromatic tetracarboxylic acid or its dianhydride and an aromatic diamine compound represented by the following general formula (■). The present invention also provides an organic solvent-soluble photosensitive polyamideimide obtained by this method.

Since the polyamide-imide of the present invention has a photosensitive unsaturated bond and a heat-resistant amide-imide ° bond in the main chain,
It has high photosensitivity and high heat resistance, and is soluble in organic solvents and various photopolymerization initiators, making it extremely suitable for forming relief patterns.

The polyamide of the present invention is a photosensitive polyamic acid (
Since it does not require an imidization step unlike polyimide precursors, it not only simplifies the process, but also has the effect of not applying distortion or stress due to thermal effects or shrinkage on the device.

The photosensitive polyamideimide of the present invention will be described in detail below along with its synthesis method.

The photosensitive polyamideimide of the present invention can be prepared by combining, for example, an aromatic tetracarboxylic acid or its dianhydride and the general formula (1).
) is synthesized by polymerizing an aromatic diamine compound having a cinnamamide bond to obtain a polyamideimide precursor, and further dehydrating and ring-closing the polyamideimide precursor (imidization).

"Used for the synthesis of the photosensitive polyamideimide of the present invention"
Specific examples of the diaromatic tetracarboxylic acid or its dianhydride include 3.3', 4.4'-biphenyltetracarboxylic acid or its dianhydride, 2,2", 3.3"
'-Biphenyltetracarboxylic acid, or its dianhydride, 2.3.3''.

4'-biphenyltetracarboxylic acid or its dianhydride, 2,3,3',4'-benzophenonetetracarboxylic acid or its dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid or its dianhydride, and pyromellitic acid or its dianhydride, and may also be an esterified product or salt of the above tetracarboxylic acid, but biphenyltetracarboxylic dianhydride is particularly preferred.

Further, specific examples of the aromatic diamine compound represented by the general formula (I) include the following.

4.4"--m-diaminocinnamanilide, 3".

4-diaminocinnamanilide, 3,4'-diaminocinnamanilide, 3.3°-diaminocinnamanilide, 2,2°-diaminocinnamanilide, etc., and the above aromatic diamine compounds in which the hydrogen of the benzene ring is methyl. Those substituted with groups, such as 4°-methyl-3'', 4-diaminocinnamanilide.

The photosensitive polyamide-imide of the present invention has a logarithmic viscosity of 0.5 g measured at 30°C as a solution having a concentration of 0.5 g of polyamide-imide/100 ml of N-methyl-2-pyrrolidone.
It is preferably within the range of 1 to 1.5, particularly 0.2 to 1.0.

To further explain the synthesis of the polyamideimide of the present invention, the aromatic tetracarboxylic acid or its dianhydride and the aromatic diamine compound are used in approximately equimolar ratios during synthesis, and their synthesis reaction is as follows: It is preferable to carry out a two-step reaction in which a polymerization reaction is first carried out and then an imidization reaction is carried out at a relatively low temperature.

That is, first, the temperature is lower than 100°C, preferably 8°C in an organic solvent.
A polymerization reaction is carried out at a reaction temperature of 0°C or lower for 1 to 48 hours, and then, after diluting the polyamideimide precursor solution obtained by this polymerization reaction with an organic solvent, the polymerization reaction is carried out at a reaction temperature of 100°C or lower, preferably 80°C or lower. acetic anhydride, pyridine,
It is preferable to add an imidizing agent such as a tertiary amine or monomer to carry out the imidization reaction for 0.5 to 5 hours, and as a result, the polyamide-imide of the present invention is synthesized.

Examples of the organic solvent in the polymerization reaction and the imidization reaction include N,N-dimethylsulfoxide-1N,
N-dimethylborumamide, N,N-diethylborumamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoramide, and the like are used.

Incidentally, the polyamide-imide of the present invention is prepared by combining the aromatic tetracarboxylic acid or its dianhydride and the aromatic diamine compound in an organic solvent at a temperature of 100°C or higher. Although C can also be synthesized by carrying out the polymerization/imidization reaction in one step in R, a stable product can be obtained by carrying out the reaction in two steps as described above.

When the photosensitive polyamideimide of the present invention is used as a material for forming a relief pattern, it is used as a solution dissolved in an organic solvent.

This #B, as a solvent, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide,
N-methyl-2-pyrrolidone, dimethyl sulfoxide,
Examples include hexamethylphosphoamide, and the preferred concentration of the photosensitive polyamideimide melt is 5 to 30.
%.

Furthermore, a sensitizer, a photopolymerization initiator, and a light-polymerizable compound having an ethylenically unsaturated group can be added to the photosensitive polyamide-imide solution, if necessary.

Examples of the sensitizer and photopolymerization initiator include Michler's ketone, benzoin, benzoin methyl ether, hendiine ethyl ether, hendiine isopropyl ether,
2-t-butylanthraquinone, 1,2-benzo-9,
Examples include 10-anthraquinone, 4,4'-bis(diethylamino)henzophenone, acetophenone, benzophenone, thioxanthone, 1,5-acenaphthene, N-acetyl-4-nitro-1-naphthylamine, and the amount added. It is preferably 0.1 to 10 parts by weight per 100 parts by weight of the photosensitive polyamideimide.

In addition, examples of the photopolymerizable compounds having ethylenically unsaturated groups include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ), rumethylolbrobantri( meth)acrylate, tetramethylolmethanetetra(meth)acrylate, N.

Examples include N''-methylenebis(meth)acrylate and diethylaminoethyl(meth)acrylate.

According to the photosensitive polyamideimide of the present invention, a relief pattern can be formed in the following manner by adjusting the photosensitive polyamideimide solution as described above.

That is, first, the above-mentioned photosensitive polyamideimide solution is applied to a substrate and dried to remove the organic solvent. Coating onto the substrate can be performed using, for example, a rotary coater. The coating film is dried at a temperature of 150°C or lower, preferably 100°C or lower. At this time, the pressure may or may not be reduced. After drying, place a negative photomask chart on the coated film and expose it to ultraviolet light,
Irradiate with active light such as visible light, electron beams, and X-rays. The unexposed areas are then washed away with a developer to obtain a polyamide-imide relief pattern. The above developer may be a solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, or hexamethylphosphoamide, or a mixture of the solvent and methanol or ethanol. can be used.

As described above, the photosensitive polyamideimide of the present invention is produced by polymerizing and imitating an aromatic tetracarboxylic acid or its dianhydride and an aromatic diamine compound represented by the general formula (I) having a cinnamamide bond. Because it is obtained by polymerization, it has a predetermined amount of photosensitive groups (photopolymerizable groups) in the main chain of the polymer, and is soluble in organic solvents, so it is easy to create relief patterns by photochemical means. When a relief pattern is formed, the polyamideimide of the present invention has high heat resistance as well as photosensitivity, and can be easily subjected to an imidization process like photosensitive polyamic acid (polyimide 1' precursor). Since this is not necessary, it not only simplifies the process, but also has many excellent effects such as no thermal influence on the element, no strain or stress due to shrinkage, etc.

Furthermore, the relief pattern formed using the photosensitive polyamide-imide of the present invention has excellent heat resistance, electrical properties, and mechanical properties, and is effective as an insulating film or a passivation film for solid-state devices in the semiconductor industry. It can also be used as an insulating film or solder resist for multilayer wiring structures in hybrid circuits and printed circuits.

Examples illustrating the synthesis of the photosensitive polyamideimide of the present invention and various physical property tests showing the effects of the photosensitive polyamideimide of the present invention and their results are listed below.

Example I 2 in 5.2 ml of N-methyl-2-pyrrolidone (NMP)
．． 710 mg of 3,3"4'-biphenyltetracarboxylic dianhydride and 6 of 3',4-diaminocinnamanilide
10 mg was added, and the mixture was stirred and reacted at 30° C. for 5 hours to obtain polyamic acid.

Next, after adding 19.4 ml of NMP and diluting the polyamic acid, 5.0 g of acetic anhydride, 1.9 g of pyridine,
Benzene 3. ' Add 8 ml and 3.2 ml of NMP,
The mixture was reacted at 0° C. for 2 hours to obtain an amide imide compound.

Add methanol dropwise into the amide imidide solution,
Polyamideimide was precipitated and separated by filtration to obtain yellow polyamideimide powder (polyamideimide of the present invention).

Example 2 Polyamide [° I got imide.

Example 3 The present invention was carried out in the same manner as in Example 1 except that 4"-methyl-3',4-diaminocinnamanilide was used instead of 3',4-diaminocinnamanilide used in Example 1. of polyamideimide was obtained.

Physical property test 1 The following physical property tests (1) to (6) were conducted on the polyamide-imide obtained in Examples 1 to 3, and the results are shown in the table below.
? It was.

(1) Viscosity of polyamide-imide The logarithmic viscosity of a polyamide-imide solution having a concentration of 0.5 g of polyamide-imide/100 ml of NMP was measured at 30°C.

(2) Film forming properties of polyamide-imide A polyamide-imide film with a thickness of about 10 μm was created on a glass plate, immersed in water, peeled off, and bent at 180 degrees. , Those in which cranking occurred during film formation were marked as ×.

(3) Solubility of polyamide-imide in NMP Solubility of polyamide-imide in NMP at room temperature (wt
%) was measured.

(4) Solubility of polyamide-imide film A polyamide-imide film with a thickness of approximately 10μ prepared from a 1B% solution of polyamide-imide in NMP is immersed in NMP at room temperature and stirred, and the solubility is measured by the time it takes for the film to melt. did.

(5) Starting temperature of thermal decomposition The starting temperature of weight loss was measured using a differential thermobalance TG-DSC manufactured by Rigaku Denki@.

(6) Photocuring properties A 10% NMP solution of polyamideimide was applied onto a glass plate using a spin coater (20'00 to 5000 rpm), and dried at 50°C for 5 hours under reduced pressure of 1 to 2 mmHH. A thin film having a thickness of several μm (see the table below) was prepared using the following methods, and this thin film was subjected to the following photosensitivity and resolution tests.

■Photosensitivity The above thin film was coated with an ultra-high pressure mercury lamp (jet light 2kW) at an illuminance of 7.2mW/cta (350mμ).
The amount of light irradiation until photocuring (, J
/cnl) was measured.

■Resolution - Thin film test chart Toppan Printing G wooden negative type test chart (Tosopan test chart N,
A relief pattern was formed using a minimum line diameter of 0.98±0.25μ), and the quality of the pattern was determined.

-1(

Claims (3)

[Claims] (1) aromatic tetracarboxylic acid or its dianhydride;
An organic solvent-soluble photosensitive polyamide-imide obtained by polymerizing and imidizing an aromatic diamine compound represented by the following general formula (I). (2) aromatic tetracarboxylic acid or its dianhydride,
3,3", 4.4'-biphenyltetracarboxylic acid or its dianhydride, 2.2', 3,3°-biphenyltetracarboxylic acid or its dianhydride, 2,3,3°
, 4′-biphenyltetracarboxylic acid, or its dianhydride, 2.3,3”, 4′-benzophenonetetracarboxylic acid, or its dianhydride, 3.3′, 4.4”-
The organic solvent-soluble photosensitive polyamideimide according to claim 11, which is benzophenonetetracarboxylic acid or its dianhydride, and pyromellitic acid or its dianhydride. (3) The aromatic diamine compound is 4.4°-diaminocinnamanilide, 3′,4-diaminocinnamanilide, 3.4′-diaminocinnamanilide, 3,3′-diaminocinnamanilide, 2 The organic solvent-soluble photosensitive polyamideimide according to claim 11, which is 2°-diaminocinnamanilide and 4''-methyl-3,4-diaminocinnamanilide.