JPH0334489B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel polyimide compounds. In general, polyimide compounds exhibit very excellent heat resistance and are extremely useful as raw materials for films, electric wire coatings, adhesives, paints, etc. that are used at high temperatures. Conventional polyimide compounds include aromatic tetracarboxylic dianhydride such as pyromellitic anhydride and diamine, N,N-dimethylformamide,
N,N-dimethylacetamide, N-methyl-2
- Aromatic polyimide compounds obtained by reacting in a solvent such as pyrrolidone to obtain a polyamic acid and then dehydrating and ring-closing this by a method such as heating are known. However, in conventional aromatic polyimide compounds, the stability of the aromatic polyamic acid, which is the precursor thereof, is poor. For example, if imidization due to dehydration and ring closure progresses even slightly, it becomes insoluble in the solvent, and when stored in a solution state for a long period of time, it becomes cloudy. There is a drawback. In order to eliminate this drawback, conventional solutions of aromatic polyamic acids usually need to be stored at 10° C. or lower, making handling extremely inconvenient. Further, conventional aromatic polyimides are unsuitable for general-purpose use because the raw material, aromatic tetracarboxylic acid, is expensive. The present inventors conducted extensive research to improve the above drawbacks, and found that a specific polyamic acid is soluble in a solvent even if partially imidized, so it is extremely stable in a solution state and has good workability. Furthermore, the present invention was achieved based on the discovery that a polyimide compound obtained by dehydrating and ring-closing the polyamic acid has excellent heat resistance, mechanical properties, electrical properties, chemical resistance, etc. An object of the present invention is to provide a polyimide compound having excellent heat resistance, mechanical properties, electrical properties, chemical resistance, etc., and a method for producing the same. The novel polyimide compound according to the present invention is characterized by having a structure represented by the following general formula (). (In the formula, R ₁ is a divalent aromatic group or an aliphatic or alicyclic hydrocarbon group, R ₂ and R ₃ are the same or different hydrogen or hydrocarbon groups, n is 10 to
Indicates an integer of 5000. ) The polyimide compound represented by the above general formula () is a tetracarboxylic dianhydride represented by the following general formula (), (In the formula, R ₂ and R ₃ are the same or different groups,
(representing a hydrogen or hydrocarbon group) and an aromatic, aliphatic, or alicyclic diamine in a solvent that dissolves at least one of them to produce polyamic acid, which is a precursor of polyimide, and the polyamic acid Obtained by heat treatment. For example, R ₁ in the polyimide compound represented by the above general formula () is

【formula】

【formula】

[Formula] (wherein, X ₁ , X ₂ , X ₃ and X ₄ are the same or different and are H or CH ₃ , and Y is CH ₂ , C ₂ H ₄ , O,
S, SO ₂ , or CONH, and n is 0 or 1
shows. ), and divalent aliphatic or alicyclic hydrocarbon groups having 6 to 13 carbon atoms.

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] −(CH ₂ ) ₆ −, −(CH ₂ ) ₇ −, −(CH ₂ ) ₈ −, −(CH ₂ ) ₉ −

【formula】

【formula】

【formula】

【formula】

[Formula] etc. can be mentioned. Further, as R ₂ , for example, -H or -CH ₃ , -
Examples include hydrocarbon groups having 1 _to 4 carbon atoms such _{as C2H5} , _-C3H7 , _{and -C4H9} . Further, from the viewpoint of ease of synthesis, n is 10 to 5,000, preferably 20 to 1,000. The tetracarboxylic dianhydride represented by the above general formula () used as a raw material in the present invention can be obtained from, for example, cyclopentadiene and maleic anhydride.

[Formula] and

It can be produced by a Friedel-Crafts reaction of the formula (R ₂ and R ₃ are the same as above). In addition, the diamine to be reacted with the tetracarboxylic dianhydride represented by the above general formula () has the general formula
It is a compound represented by H ₂ N-R ₁ -NH ₂ (wherein R ₁ is the same as above). Specific examples of these include paraphenylenediamine, metaphenylenediamine, 4,4'-diaminodiphenylmethane, 4,
4'-diaminodiphenylethane, penzidine,
4,4'-diaminodiphenyl sulfide, 4,
4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,4'-diaminobenzanilide,
3,4'-diaminodiphenyl ether, metaxylylene diamine, paraxylylene diamine, hexamethylene diamine, heptamethylene diamine,
Octamethylene diamine, nonamethylene diamine, 4,4'-dimethylheptamethylene diamine,
3-methoxyheptamethylene diamine, 1,4-
Diaminocyclohexane, tetrahydrodicyclopentadienylenediamine, hexahydro-4,
Examples include 7-methanoindani dimethylene diamine, tricyclo[6,2,1,o ^2.7 ]-undecylene dimethylene diamine, and the like. These can be used alone or in combination. N
-N-alkylpyrrolidones such as methyl-2-pyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide, and N,N-dialkylamides are preferred, but alcohols, which are common organic solvents, Phenols, ketones, ethers such as ethyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, phenol, cresol, methyl ethyl ketone, tetrahydrofuran, etc. may also be used. I can do it. The reaction ratio of the tetracarboxylic dianhydride represented by the above general formula () and the diamine is preferably carried out in equimolar amounts, but there may be a slight excess or deficiency as long as the purpose of the present invention is achieved. Further, although it is usually preferable to carry out the reaction in the above-mentioned solvent, it is possible to carry out the reaction without using a solvent. The amount of the solvent used is preferably 0.5 parts by weight per 100 parts by weight of the tetracarboxylic dianhydride and diamine represented by the general formula ().
~20 times the weight. The reaction temperature for producing polyamic acid, which is a precursor of the polyimide compound of the present invention, is generally 20°C.
~100°C is preferred. The polyamic acid obtained as a precursor of the polyimide compound of the present invention is easily soluble in a solvent, and even if a part of the polyamide is imidized, it is soluble in the solvent.
Very stable in solution. Next, to produce a polyimide compound by dehydrating and ring-closing polyamic acid, generally the polyamic acid solution obtained by the above reaction is heated as is, or the polyamic acid is coagulated in a non-solvent for polyamic acid (e.g. acetone). After that, the coagulated polyamic acid is heated to undergo dehydration and cyclization, or the coagulated polyamic acid is redissolved in a solvent and heated to evaporate the solvent while dehydration and cyclization is performed. The preferred heating temperature is 100-500°C. The intrinsic viscosity of the polyamic acid before heating ([η] 30°C N-methyl-2-pyrrolidone) is preferably 0.05 dl/g or more, particularly preferably 0.05 to 5 dl/g, and the degree of polymerization n of the polyamic acid is 10 ~5000. The degree of polymerization n of this polyamic acid corresponds to the degree of polymerization n of the polyimide compound represented by the above general formula (). Stabilizers such as antioxidants are added to the above polyamic acid.
For example, 0.01 to 5 parts per 100 parts by weight of polyamic acid
Additives such as fillers may be added in an amount of about 1 part by weight, for example, 1 part by weight per 100 parts by weight of polyamic acid.
About 100 parts by weight may be added. The method for molding the polyimide compound of the present invention varies depending on the use of the polyimide compound, but for example, a support is coated with a polyamic acid solution, or a mat of glass fiber, carbon fiber, etc. is impregnated, and then the polyimide compound is gradually added. By heating and finally heating to 250 to 400°C, a transparent and tough film or fiber-reinforced sheet of polyimide compound can be obtained. The novel polyimide compound according to the present invention exhibits excellent properties such as heat resistance, mechanical properties, electrical properties, and chemical resistance, and is useful for, for example, high-temperature films, adhesives, paints, etc. Specifically, it is useful for printing It is useful for wiring boards, flexible wiring boards, surface protection films or interlayer insulating films for semiconductor integrated circuit elements, covering materials for enameled electric wires, various laminates, gaskets, etc. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 (1) Synthesis of raw material tetracarboxylic dianhydride 695 g of dicyclopentadiene, 501 g of maleic anhydride, and 1180 g of xylene were charged into a nitrogen (N ₂ )-substituted autoclave, and a reaction was carried out at 230° C. for 3 hours. The reaction solution was distilled under reduced pressure to 180~2mHg.
700g of a boiling point fraction at 200℃ was obtained, and the 700g was further rectified to obtain a 2/1 adduct of cyclopentadiene and maleic anhydride.

300g of [Formula] () was obtained. Next, put 100g of the above compound () and 80g of toluene into a flask with a condenser that was replaced with _N2 ,
6 g of boron trifluoride (BF ₃ ) phenol complex (30% concentration by weight) at 80°C with stirring
was added dropwise over 10 minutes, and the alkylation reaction was carried out for a total of 1 hour. Analysis of the reaction solution using GPC (gel permeation chromatography) revealed that, other than toluene, 60% of the compound () was alkylated with 1/1 of toluene, and 60% was alkylated with 2/1 of toluene. 30%, and the heavy content was 10% (% indicates the area ratio of GPC). A powder with the above composition obtained by distilling off toluene from the alkylation reaction solution was dissolved in acetone and recrystallized to obtain a white powder compound () with a melting point of 216°C.
I got it. The infrared absorption spectrum of the compound () is shown in FIG. 1, and absorption based on -C=0 of the anhydride was observed at 1780 and 1860 cm ^-1 . Further, this was hydrolyzed using sodium hydroxide and back-titrated using hydrochloric acid, and the yield was 7.23 mg equivalent/g. In addition, the nuclear magnetic resonance spectrum of compound () is shown in Figure 2, and toluene

Proton absorption based on [Formula] was observed at 2.4τ. The compound () obtained above was a tetracarboxylic dianhydride which is a 2/1 alkylated product of the compound () shown by the following formula and toluene. (Theoretical acid equivalent: 7.25 mg equivalent/g) (2) Production of polyimide compound Under _N2 atmosphere, 9.9 g (0.05 mol) of 4,4'-diaminodiphenylmethane was added to 200 ml of N-methyl-2-pyrrolidone (NMP). Dissolve the compound () obtained in section (1) above at 25℃ with stirring.
After adding 27.5g (0.05mol) and suspending, 80
The temperature was raised to ℃ and allowed to react for 1 hour. Thereafter, this reaction solution was poured into acetone, coagulated, and dried to obtain 36 g of polyamic acid powder. Intrinsic viscosity [η] of this polyamic acid (30℃,
(in NMP solvent) was 0.47 dl/g. Note that even when the solution after the reaction was left at 25°C for 30 days, there was no increase in viscosity, and no phenomena of insoluble analysis such as white turbidity were observed. Next, 10g of this polyamic acid powder was added to N,N-
Dissolve in 40 g of dimethylformamide to make a 20% by weight solution, spin coat a portion on a glass plate, heat at 120°C for 1 hour, and at 200°C for 1 hour.
A transparent polyimide compound film of 20 μm was prepared by heat treatment at 350° C. for 30 minutes. The infrared absorption spectrum of this polyimide compound was
As shown in the figure, absorption based on imidocarbonyl was observed at 1780 cm ^-1 . In addition, as a result of elemental analysis of the above polyimide compound, 80.3% carbon,
6.3% hydrogen, 4.1% nitrogen, 9.3% oxygen (calculated values: 80.7% carbon, 6.4% hydrogen, 3.9% nitrogen, 9.0% oxygen)
It was hot. From the above, the structure of the polyimide compound obtained in this example is It was determined that Example 2 (1) Synthesis of raw material tetracarboxylic dianhydride (R ₂ is CH ₃ and R ₃ is CH ₃ in general formula ()) In Example 1, p-
The same reaction as in Example 1 was carried out except that 94 g of xylene was used. Analysis of the reaction solution using GPC revealed that, other than p-xylene, compound () and p-xylene had a 1/1 alkylated product of 25%, a 2/1 alkylated product of 65%, and a heavy content of 10%. %(%teeth
(indicates the area ratio of GPC). After distilling off p-xylene from the above reaction solution,
The reaction mixture was recrystallized (twice) from acetone to obtain a white powder compound () with a melting point of 300°C or higher (yellowing from around 320°C). Compound()
Figure 4 shows the infrared absorption spectrum of
Absorption based on -C=O of anhydride was observed at 1785 and 1867 cm ^-1 . Moreover, the acid equivalent of this was 7.10 mg equivalent/g. From this result, the obtained compound () was a tetracarboxylic dianhydride which is a 2/1 alkylated product of the compound () shown by the following formula and p-xylene. (Theoretical acid equivalent: 7.06 mg equivalent/g) (2) Production of polyimide compound In the production of the polyimide compound of Example 1, 28.3 g of tetracarboxylic dianhydride () was used instead of tetracarboxylic dianhydride ().
The same reaction as in Example 1 was carried out except that (0.05 mol) was used. Thereafter, this reaction solution was poured into acetone, coagulated, and dried to obtain 35 g of polyamic acid powder. Intrinsic viscosity [η] of this polyamic acid (30℃,
(in NMP solvent) was 0.57 dl/g. Note that even when the solution after the reaction was left at 25°C for 30 days, there was no increase in viscosity, and no insoluble analysis such as cloudiness was observed. Next, 10g of this polyamic acid powder was added to N,N-
Dissolved in 40g of dimethylformamide, 20% by weight
Prepare a solution, spin coat a portion onto a glass plate, heat at 120°C for 1 hour, and at 200°C for 1 hour.
A 20 μm transparent polyimide film was produced by heat treatment at 350°C for 30 minutes. The infrared absorption spectrum of this polyimide compound is shown in FIG. 5, and absorption due to imide carbonyl was observed at 1775 cm ^-1 . In addition, as a result of elemental analysis of the above polyimide compound, carbon 80.2
%, hydrogen 6.4%, nitrogen 4.2%, oxygen 9.2% (calculated values: carbon 80.7%, hydrogen 6.6%, nitrogen 3.84%, oxygen
8.8%). From the above, the structure of the polyimide compound obtained in this example is It was determined that Example 3 In Example 1, hexamethylene diamine was used instead of 4,4'-diaminodiphenylmethane.
The same reaction as in Example 1 was carried out except that 5.8 g (0.05 mol) was used. Thereafter, this reaction solution was poured into acetone, coagulated, and dried to obtain 32 g of polyamic acid powder. Intrinsic viscosity [η] of this polyamic acid (30℃,
(in NMP solvent containing 0.02 wt% NaCl) is 0.44 dl/g
It was hot. Note that even when the solution after the reaction was left at 25°C for 30 days, there was no increase in viscosity, and no phenomena of insoluble analysis such as white turbidity were observed. Next, 10 g of this polyamic acid powder was dissolved in 40 g of N,N-dimethylformamide to make a 20% solution by weight, and a portion was spin coated on a glass plate at 120°C for 1 hour and at 200°C for 1 hour. , at 350℃
A 20 μm transparent polyimide compound film was prepared by heat treatment for 30 minutes. The infrared absorption spectrum of this polyimide compound is shown in FIG. 6, and absorption due to imide carbonyl was observed at 1775 cm ^-1 . In addition, as a result of elemental analysis of the above polyimide compound, carbon 77.5%, hydrogen 7.5%, nitrogen 4.6%, oxygen 10.4% (calculated value: carbon
77.9%, hydrogen 7.6%, nitrogen 4.4%, oxygen 10.1%). From the above, the structure of the polyimide compound obtained in this example is It was determined that Example 4 In place of 4,4'-diaminodiphenylmethane in Example 1, 9.7 g of hexahydro-4,7-methanoindani dimethylenediamine was used.
The same reaction as in Example 1 was carried out except that (0.05 mol) was used. This reaction solution is then poured into acetone to solidify and dry to form polyamic acid powder.
Obtained 36g. The intrinsic viscosity of this polyamic acid compound [η] (30
°C, in NMP solvent containing 0.02 wt% NaCl) is 0.4
It was dl/g. Note that even when the solution after the reaction was left at 25°C for 30 days, there was no increase in viscosity, and no phenomena of insoluble analysis such as white turbidity were observed. Next, 10 g of this polyamic acid powder was dissolved in 40 g of N,N-dimethylformamide to make a 20% solution by weight, and a portion was spin coated on a glass plate at 120°C for 1 hour and at 200°C for 1 hour. , at 350℃
A 20 μm transparent polyimide compound film was prepared by heat treatment for 30 minutes. The infrared absorption spectrum of this polyimide compound is shown in FIG. 7, and absorption due to imide carbonyl was observed at 1770 cm ^-1 . In addition, as a result of elemental analysis of the above polyimide compound, carbon 79.1%, hydrogen 7.5%, nitrogen 4.1%, oxygen 9.3% (calculated value: carbon
79.5%, hydrogen 7.6%, nitrogen 3.9%, oxygen 9.0%). From the above, the structure of the polyimide compound obtained in this example is It was determined that Example 5 The reaction was carried out in the same manner as in Example 1, except that 10.0 g (0.05 mol) of 4,4'-diaminodiphenyl ether was used instead of 4,4'-diaminodiphenylmethane. . Thereafter, this reaction solution was poured into acetone, coagulated, and dried to obtain 34 g of polyamic acid powder. Intrinsic viscosity [η] of this polyamic acid (30℃,
(in NMP solvent) was 0.52 dl/g. Note that even when the solution after the reaction was left at 25°C for 30 days, there was no increase in viscosity, and no phenomenon of cloudy insoluble analysis was observed. Next, 10 g of this polyamic acid powder was dissolved in 40 g of N,N-dimethylformamide to make a 20% solution by weight, and a portion was spin coated on a glass plate at 120°C for 1 hour and at 200°C for 1 hour. , at 350℃
A 20 μm transparent polyimide compound film was prepared by heat treatment for 30 minutes. The infrared absorption spectrum of this polyimide compound is shown in FIG. 8, and absorption due to imide carbonyl was observed at 1780 cm ^-1 . Furthermore, when performing elemental analysis of the above polyimide compound, carbon 78.3%, hydrogen 6.5%, nitrogen 3.7%, oxygen 11.6% (calculated values: carbon 78.7%, hydrogen 6.2%, nitrogen
3.9%, oxygen 11.2%). From the above, the structure of the polyimide compound obtained in this example is: It was determined that Example 6 In Example 1, tetracarboxylic dianhydride () was used instead of tetracarboxylic dianhydride ().
The reaction was carried out in the same manner as in Example 1, except that 10.0 g (0.05 mol) of 4,4'-diaminodiphenyl ether was used instead of 28.3 g (0.05 mol) and 4,4'-diaminodiphenylmethane. Thereafter, this reaction solution was poured into acetone, coagulated, and dried to obtain 35.5 g of polyamic acid powder. Intrinsic viscosity [η] of this polyamic acid (30℃,
(in NMP solvent) was 0.68 dl/g. Note that even when the solution after the reaction was left at 25°C for 30 days, there was no increase in viscosity, and no insoluble analysis such as cloudiness was observed. Next, 10 g of this polyamic acid powder was dissolved in 40 g of N,N-dimethylformamide to make a 20% solution by weight, and a portion was spin coated on a glass plate at 120°C for 1 hour and at 200°C for 1 hour. , at 350℃
A 20 μm transparent polyimide film was produced by heat treatment for 30 minutes. The infrared absorption spectrum of this polyimide compound is shown in FIG. 9, and absorption due to imide carbonyl was observed at 1780 cm ^-1 . In addition, elemental analysis of the above polyimide compound revealed that 78.2%, hydrogen 6.4%,
The content was 4.3% nitrogen and 11.1% oxygen (calculated values: 78.9% carbon, 6.3% hydrogen, 3.8% nitrogen, and 10.9% oxygen). From the above, the structure of the polyimide compound obtained in this example is It was determined that Example 7 In Example 1, N,N-dimethylformamide was used instead of N-methyl-2-pyrrolidone.
The reaction was carried out in the same manner as in Example 1 except that 200 ml was used. The weight of the obtained polyamic acid was 30.5 g, and the intrinsic viscosity [η] (30°C, in NMP solvent) was 0.42.
It was dl/g. The infrared absorption spectrum of the polyimide obtained from this polyamic acid matched that shown in FIG. Example 8 In Example 1, N,N-dimethylacetamide was used instead of N-methyl-2-pyrrolidone.
The reaction was carried out in the same manner as in Example 1 except that 200 ml was used. The weight of the obtained polyamic acid was 31.5 g, and the intrinsic viscosity [η] (30°C, in NMP solvent) was 0.46.
It was dl/g. The infrared absorption spectrum of the polyimide obtained from this polyamic acid matched that shown in FIG.

[Brief explanation of drawings]

Figures 1 and 4 are diagrams showing the infrared absorption spectrum of tetracarboxylic dianhydride, which is the raw material of the present invention, Figure 2 is a diagram showing its nuclear magnetic resonance spectrum, Figures 3 and 5. Figure, Figure 6, Figure 7, Figure 8
9 and 9 are diagrams showing infrared absorption spectra of polyimide compounds obtained in Examples of the present invention, respectively.

Claims (1)

[Claims] 1. A polyimide compound represented by the following general formula () (In the formula, R ₁ is a divalent aromatic group or an aliphatic or alicyclic hydrocarbon group, R ₂ and R ₃ are the same or different groups, and are hydrogen or hydrocarbon groups, and n is 10
~5000 integers).