JPS59108751A - Novel diacrylamido aromatic diamine compound - Google Patents

Abstract

NEW MATERIAL:A diacrylamido aromatic diamine compound shown by the formula I . EXAMPLE:3,4'-Acrylamido-3',4-diaminodiphenyl ether. USE:A raw material for synthesizing a photosensitive aromatic polyimide soluble in an organic solvent. For example, it is polymerized with biphenyltetracarboxylic acid dianhydride, a specific aromatic tetracarboxylic acid to give a polyamic acid, which is further subjected to ring closure through dehydration(imidation), to give a photosensitive polyimide containing a unit, shown by the formula II, soluble in an organic solvent. PROCESS:Diaminodiphenyl ether is acetylated with acetic anhydride to give diacetylamidodiphenyl ether, which is nitrated with fuming nitric acid, and hydrolyzed to give diaminodinitrodiphenyl ether, which is reacted with acrylic chloride to give diacrylamidodiphenyl ether, which is reduced to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel diacrylamide aromatic diamine compound, and the novel diacrylamide aromatic diamine compound of the present invention is useful as a raw material for the synthesis of organic solvent-soluble photosensitive aromatic polyimide. It is something.

BACKGROUND ART In the semiconductor industry, materials for forming insulating films and pannosification films on solid-state devices, and insulating materials for semiconductor integrated circuits, multilayer printed wiring boards, etc., are required to have high heat resistance and insulation properties. From this point of view, various proposals have been made to form the above-mentioned panshyhesion film etc. with polyimide, which has high insulation and heat resistance (Japanese Patent Application Laid-Open No. 4/9-11).
5541, JP 54-116216, JP 54-116217, and JP 56-459.
(See Publication No. 15, etc.)

However, polyimide does not have a photosensitive group, and in the above proposal, the polymer containing a photosensitive group is all in the form of polyamic acid, which is a polyimide precursor, and the polyamic acid is imidized after photocuring. Therefore, it is necessary to use polyimide.

7. The present invention provides a raw material for organic solvent-soluble photosensitive polyimide suitable for forming relief patterns. The object of the present invention is to provide a novel sia,'7lylamide aromatic diamine compound, which is useful as a 'mer, and is represented by the following formula.

0 111 The novel diacrylamide aromatic diamine compound of the present invention represented by the general formula (1) will be described in detail below.

The novel diacrylamide aromatic diamine compound of the present invention has a form in which an acrylamide group is attached as a substituent to each of the two Hensen rings of diaminodiphenyl ether, as is clear from the above general formula [■]. Examples include the following compounds:

(113,4'-acrylamide-3',4-diaminodiphenyl ether (2+3.3°-acrylamide-4,4''-diaminodiphenyl ether)Next, a representative synthesis method for the novel diacrylamide aromatic diamine compound of the present invention List.

A typical method for synthesizing the novel diacrylamide aromatic diamine compound of the present invention consists of the following five steps (1) to (2).

■ Add acetic anhydride to diaminodiphenyl ether and acetylate it to synthesize diacetylamide diphenyl ether.

■Add diacetylamide diphenyl ether to fuming nitric acid and nitrate to synthesize diacetylamide dinitrodiphenyl ether.

■ Hydrolyze diacetylamide dinitrodiphenyl ether to obtain diamino dinitrodiphenyl ether.

■Diamino dinitrodiphenyl ether and acrylic acid chloride are reacted to synthesize diacrylamide dinitrodiphenyl ether.

(2) Finally, diacrylamide dinitrodiphenyl ether is added to a solution of iron powder suspended in acetic acid/water and reduced to obtain the diacrylamide aromatic diamine compound of the present invention.

For example, when attempting to synthesize the diacrylamide aromatic diamine compound (1) as the target product, the reaction may be carried out according to the following reaction formula.

In the above synthesis, it is not appropriate to reduce diacrylamide dinitrodiphenyl ether in a suspension of tin powder, iron powder, etc. and hydrochloric acid/water because hydrolysis of the acrylamide group will occur; The reaction of iron powder in suspension with acetic acid/water is optimal.

Therefore, the diacrylamide aromatic diamine compound of the present invention represented by the general formula (1) can be polymerized with biphenyltetracarboxylic dianhydride, which is a specific aromatic tetracarboxylic acid, to form a polyamic acid. , further by dehydrating and ring-closing the polyamic acid (imidization),
It is possible to synthesize a photosensitive polyimide that is soluble in an organic solvent and includes a structural unit represented by the following formula (II).

(In the formula, Y is -N HCCH= CH2.
-) Therefore, specific examples of the above polyimide include the following.

(However, Y is as described above.) The polyimide mentioned above has photosensitivity, and in order to maintain the heat resistance of polyimide, it is used as a separate photoresist for image formation (like conventional non-photosensitive polyimide). photopolymerizable substances)
Since it is soluble in organic solvents, it does not pose any problem in forming relief patterns.

In addition, unlike photosensitive polyamic acid (polyimide precursor), it does not require imidization, which not only simplifies the process, but also eliminates distortion and stress caused by thermal effects and shrinkage on the device. It has many excellent effects.

The synthesis of the polyimide is carried out using approximately equal moles of the biphenyltetracarboxylic dianhydride and the diacrylamide aromatic diamine compound of the present invention represented by the general formula (I) in an organic solvent. A polymerization reaction is carried out for 0.5 to 50 hours at a reaction temperature of 100°C or less, preferably 80'CU, and then the polyamic acid solution obtained by this polymerization reaction is diluted with an organic solvent and then heated to 100°C or less, Preferably, at a reaction temperature of 80°C or lower, an imidizing agent such as acetic anhydride, pyridine, or a tertiary amine is added, and the reaction temperature is 0°5 to 0.5°C.
It is preferable to carry out the imidization reaction for 5 hours.

As the organic solvent in the above polymerization reaction and the imidization reaction described in 1., for example, dimethyl sulfoxide, dibutylformamide, dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoramide, etc. are used.

The above-mentioned polyimide can also be obtained by performing a polymerization/imidization reaction of the biphenyltetracarboxylic dianhydride and the diacrylamide aromatic diamine compound of the present invention in an organic solvent at a high temperature of 100°C or higher in one step. It can be synthesized in two steps, as described above, to obtain a stable product.

When the photosensitive polyimide of the present invention is used as a material for forming a relief pattern, it is dissolved in an organic solvent and used as a solution, and the preferable concentration of the photosensitive polyimide solution is 5 to 30%.

In addition, a sensitizer, a photopolymerization initiator, or a compound having an ethylenically unsaturated group that can be dimerized by light can be added to the photosensitive polyimide solution as necessary. The amount is preferably 0.1 to 10 parts by weight per 100 parts by weight of the photosensitive polyimide.

As mentioned above, the novel diacrylamide aromatic diamine compound of the present invention is useful as a raw material monomer for organic solvent-soluble photosensitive polyimide, but it is also useful as a raw material monomer for other polyimides, polyamides, etc. It is.

Examples showing the synthesis of the diacrylamide aromatic diamine compound of the present invention are listed below, along with examples of synthesis of photosensitive polyimide and various physical property tests showing the effects of the photosensitive polyimide and their results.

Example 1 Synthesis of 3.4'-acrylamide-3',4-diaminodiphenyl ether First step 3. Acetylation of 4'-diaminodiphenyl ether Commercially available 3,4'-diaminodiphenyl ether.

56.9 g (0.28 mol) were dissolved in 1.50 ml of acetic acid and 200 ml of water and 60 g of acetic anhydride were added at 4-5°C.
(0.59 mol) was added all at once. At that time, he had a fever of 25°C. Thereafter, the mixture was heated at 50° C. for 15 minutes to advance the reaction, and then poured into 4β water to precipitate white crystals. The precipitate was filtered to obtain 80.7 g of reddish brown fine powder of 3.4'-diacetylamide diphenyl ether. (Yield 99.0%) Second step 3. Nitration of 4′-diacetylamide diphenyl ether 100 g (0.35 mol) of 3,4′-diacetylamide diphenyl ether obtained in the first step was mixed with 50 g of acetic acid.
The solution dissolved in 0 ml of fuming nitric acid (specific gravity 1.52) 1
000g dropwise at 5°C±1°C. After the dropwise addition was completed, the temperature was maintained for 10 minutes, and then the reaction solution was poured into approximately 20β water to precipitate, which was collected by filtration and dried. Purification was performed by silica gel chromatography. That is, 5
Silica gel (C-
Fill 200g of 200), place the crude product as a powder on top of it, separate it using benzene as a developing solvent,
-Diacetylamide-3',4-dinitrodiphenyl ether was fractionated to obtain 45.5 g. (Yield 35
%) Third step 3.4゛-diacetylamide-3゛, 3,4゛-diacetylamide-3゛ obtained in the second step of hydrolysis of 4-dinitrodiphenyl ether
, 45.5 g of 4-dinitrodiphenyl ether was added little by little as a powder to 150 ml of Claisen alkali (35.2 g of potassium hydroxide dissolved in 40 ml of water and then made up to 150 ml with methanol) at 70 to 80°C with stirring. Ta. After the addition was complete, the mixture was heated to 70° C. for 10 minutes.

The temperature was returned to room temperature, and the mixture was poured into 1.54 ml of ice water to precipitate crystals. The precipitate was collected by filtration and dried to obtain 25.8 g of brown powder. Purification was performed by silica gel chromatography. That is, 100 g of silica gel (C-200) was filled in a 50 mmφ x 500 ml chromatography tube, and separated using a 1:1 mixed solvent of acetic acid and benzene as a developing solvent. The elution solvent was evaporated to yield 25.4 g of a yellow-orange powder of 3,4''-dinitro-3'',4-diaminodiphenyl ether.

Fourth step 3. Acrylation of 4°-dinitro-3′,4-diaminodiphenyl ether 25.4 g (0.08 mol) of 3,4″-dinitro-3″4-diaminodiphenyl ether obtained in the third step and Acrylic acid chloride 4
7.5 g (0.53 mol) of tetrahydrofuran 1
A 50 ml/8 diluted solution was added at room temperature. At that time, he developed a fever, which rose to 31°C.

After the dropwise addition was completed, the mixture was further heated at 50 to 55°C for 1.5 hours. After the reaction was completed, the temperature was returned to room temperature and filtered under reduced pressure to obtain a filtrate and a filtrate. After concentrating the filtrate, pour it into 1.5p of water,
This was made alkaline with aqueous ammonia to precipitate a yellow flocculent material. The product was collected by filtration to obtain 1.6 g of 3,4'-diacrylamide-3',4-dinitrodiphenyl ether.

On the other hand, after pouring the filtered leaves into 1.54 g of water, a reddish-brown precipitate was produced, similar to when the filtered material was rubbed alkaline with aqueous ammonia. The residue was filtered under reduced pressure and the filtered material was dried to obtain 34.3 g of crude 3,4'-diacrylamide-3',4-dinitrodiphenyl ether. 'R crack is silica gel (C-200)
Fill a 50 mmφ x 500 ml chromatography tube with 2 oOg, and place the above-mentioned crude product on top, and perform chromatography separation using a 1:1 (vol) mixed solvent of benzene and ethyl acetate as a developing solvent to obtain 21 g of 3,4"
-diacrylamide-3'4-dinitrodiphenyl ether was obtained.

(Yield 60%) Fifth step 3. Reduction of 4"-diacrylamide-3',4-dinitro diphenyl ether 20 g of 3,4"-diacrylamide-3',4-dinitro diphenyl ether obtained in the fourth step (0,05
mol) in 300 g of acetic acid was added to 1.0 g of iron powder. OO
was added little by little to a cloudy solution of 50 g of water and IOOG of acetic acid with stirring. At that time, I had a fever, and I cooled it with water.
The reaction was carried out at around 0°C.

Add the reaction solution to 500ml of ammonia water (25%) and 5p of water.
The mixture was poured into ice water to make alkaline, extracted with ether-ethyl acetate (3:1), dried over anhydrous sodium sulfate, and the solvent was removed to obtain 10.2 g of product.

(Yield 6o%) Melting point 81-82°C Elemental analysis value C) IN Actual value 54.83 3.77 13.25 Calculated value 54.48 3.54 14.07 Also, infrared absorption spectrum of the product (see drawing), and H-N
The MR spectrum was measured and it was confirmed that it was the desired product.

Synthesis Example I N-methyl-2-pyrrolidone (NMP) 41.
Add 5.56 g of 3,3",4,4°-biphenyltetracarboxylic dianhydride and 6306 g of 3,4"-diacrylamide-3',4-diaminodiphenyl ether to 5 ml, and stir at 30'C for 20 hours. The reaction was carried out to obtain polyamic acid.

Next, 156 ml of NMP was added to dilute the polyamic acid, and then 38.6 g of acetic anhydride and 14 ml of pyridine were added.
．． 7g, benzene 30.2ml and NMP 26.
Add Oml and react at 50°C for 1 hour to form the imidide (
A photosensitive polyimide consisting of the structural unit 1) was obtained.

Methanol was added dropwise into the imidide solution to precipitate the polyimide, which was filtered off to obtain a yellow; Ji IJ imide powder.

Regarding the polyimide obtained in the synthesis example in Physical property test 1, the following +11 to (5
) was conducted and the results shown in the table below were obtained.

(1) Viscosity of polyimide The logarithmic viscosity of a polyimide solution having a concentration of 0.5 g NMP 10 Oml of polyimide was measured at 30°C.

(2) Polyimide film forming property A polyimide 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 cracks were formed during film formation were marked as ×.

(3) Solubility of polyimide film A polyimide film with a thickness of about 10 μm was immersed in NMP at room temperature and stirred, and the solubility was observed to determine whether the solubility was good or bad.

(4) Thermal decomposition start temperature The weight loss start temperature was measured using a differential thermobalance TG-DSC manufactured by Rigaku Denki@.

(5) Photo-curable properties A photosensitive polyimide solution prepared by adding 6 phr of Michler's ketone to a 10% NMP solution of polyimide was coated onto a glass plate to a thickness of several μ using a spin coater (2000-5000 rpm). (see table) and apply pressure 1 to 2.
A thin film was prepared by drying at 50° C. for 5 hours under reduced pressure of 1 g of mm, and this thin film was subjected to the following photosensitivity and resolution tests.

■Photosensitivity The above thin film is photocured by irradiating it with an ultra-high pressure mercury lamp (jet light 2kW) at an illuminance of 7.2mW/cA (350m μ), and the amount of light irradiation (J/
c) was measured.

■Resolving power As a test chart for the above thin film, a relief pattern was formed using a negative type test 1-chi-t (Tosoban Test Chart N, minimum line 0.98±0.25μ) manufactured by Toppan Printing@, and the pattern was It was judged whether it was good or bad.

[Brief explanation of the drawing]

The drawing shows a chart of an infrared absorption spectrum of a novel diacrylamide aromatic diamine compound synthesized in an example of the present invention. Patent Applicant Ube Kosan Co., Ltd. Continuing Amendment (Method) April 15, 1981 Kazuo Wakasugi, Commissioner of the Patent Office 1, Indication of Case Patent Application No. 1982-218090 2, New Title of Invention Relationship between diacrylamide aromatic cyamine compound 3 and the amended sound incident Patent application Hitoube Industries Co., Ltd. 4, Agent 601 Pacific Nogizaka, 6-29 Tokisaka 9-chome, Minato-ku, Tokyo, I03 (479) 25316, Ni positive subject application and specification all 7, contents of amendment

Claims (1)

[Claims] (A novel diacrylamide aromatic diamine compound represented by the following formula. (2) Claim (1) in which the amine group is bonded to the 3.4" position. (313,4'-diacrylamide-4,3'-diaminodiphenyl ether) The compound according to claim (1).