JPH0229690B2 - HORIAMIDOSANKAGOBUTSU - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to polyamic acid compounds. [Prior Art] In general, polyamic acid compounds are very useful as precursors for polyimide compounds that exhibit excellent heat resistance, and can be modified by reacting and mixing with various monomers and polymers. Wide range of uses. Conventional polyamic acid compounds include aromatic tetracarboxylic dianhydride such as pyromellitic anhydride and diamine in a solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. Aromatic polyamide acid compounds obtained by reacting in However, conventional aromatic polyamic acid compounds have poor storage stability, and have the drawback that, for example, if imidization due to dehydration and ring closure progresses even slightly, they become insoluble in solvents and become cloudy when stored in a solution state for a long period of time. To eliminate this drawback, conventional polyamic acid solutions usually need to be stored at temperatures below 10°C.
It was extremely inconvenient to handle. Further, conventional aromatic polyamide acid compounds were unsuitable for general use because the raw material, aromatic tetracarboxylic dianhydride, was expensive. [Problems to be Solved by the Invention] The purpose of the present invention is to solve the problems of the prior art and to provide a precursor for polyimide compounds having excellent heat resistance, mechanical properties, electrical properties, chemical resistance, etc. The object of the present invention is to provide a polyamide acid compound that is stable in a solution state. [Means for Solving the Problems] The present invention provides a structure in which two hydroxyl groups are removed from 2,3,5-tricarboxy-cyclopentane-acetic acid, and two amino acids in an aliphatic or alicyclic diamine. 30 to 100 mol% of structural units in which a structure obtained by removing one hydrogen atom from each group is bonded by an amide bond, and 0 to 70 mol% of structural units obtained by dehydration and ring closure of at least one of the amide bonds of the structural unit. The present invention provides a polyamide acid compound consisting of repeating structural units and having an intrinsic viscosity [η] (30°C, in N-methyl-2-pyrrolidone solvent) of 0.05 to 5 dl/g. In the polyamide acid compound of the present invention, a part of the amide bond is dehydrated and ring-closed, for example, the following general formula (),
A portion of repeating structural units represented by (), (), (), etc. may be present. The polyamide acid compound of the present invention is 2,3,5-
It is obtained by reacting tricarboxy-cyclopentane-acetic acid or its anhydride with an aliphatic or alicyclic diamine in a solvent that dissolves at least one of them. The 2,3,5-tricarboxy-cyclopentane-acetic acid (hereinafter referred to as "TCA") can be produced by, for example, a method in which dicyclopentadiene is ozonolyzed and oxidized with hydrogen peroxide (British Patent No.
872355, J.Org.Chem.28(10)2537, 1963), oxidation of hydroxy-dicyclopentadiene obtained by hydrating dicyclopentadiene with nitric acid (West German Patent No. 1078120), etc. By dehydrating TCA, an anhydride (usually dianhydride) of TCA can be obtained. The diamine to be reacted with _{the TCA or TCA anhydride is a compound represented by the general formula: H2NR1-NH2 , where R1} is a divalent aliphatic or alicyclic group. For this R ₁ , −(CH ₂ ) ₆ −, −(CH ₂ ) ₇
−, −(CH ₂ ) ₈ −, −(CH ₂ ) ₉ −,

【formula】

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〔Example〕

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 11.6 g of hexamethylene diamine under _N2 atmosphere
(0.1 mol) in 200 ml of N-methyl-2-pyrrolidone (NMP) and heated at 25°C with stirring.
After adding and suspending 22.4 g (0.1 mol) of TCA2 anhydride, the temperature was raised to 50° C. and the mixture was reacted for 3 hours. Thereafter, this reaction solution was poured into acetone, coagulated, and dried to obtain 33 g of polyamide acid compound powder. The intrinsic viscosity of this polyamic acid compound η (30℃,
(in NMP solvent) was 1.4 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 clouding were observed. The infrared absorption spectrum of the above polyamic acid compound is shown in FIG. 1, and absorption due to amide carbonyl was observed at 1640 cm ^-1 . Further, the -COOH group content of the polyamide acid compound was determined by alkaline titration, and the imidization rate was measured from this -COOH group content, and the imidization rate was 0%. In addition, the imidization rate in this case is the ratio of imide bonds (expressed in mol%) when the total amount of amide bonds and imide bonds (bonds formed by dehydration and ring closure of amide bonds) in the polyamic acid compound is 100. This is what is shown. In addition, as a result of elemental analysis of the above polyamide acid compound, carbon 56.1%, hydrogen 7.0%, nitrogen 8.4%
(Calculated values: 56.5% carbon, 7.1% hydrogen, 8.2% nitrogen). Next, 10g of powder of this polyamic acid compound was added to N,
Dissolve in 30 g of N-dimethylformamide to make a 25% 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.
Heat treatment was performed at 350°C for 30 minutes to produce a 20 μm brown transparent polyimide compound film. When various physical properties of this compound were measured, the results shown in Table 1 were obtained.

〔Effect of the invention〕

The polyamic acid compound of the present invention has excellent storage stability, and the polyimide compound using the polyamic acid compound as a precursor exhibits excellent properties such as heat resistance, mechanical properties, electrical properties, and chemical resistance properties.
For example, it is useful for high-temperature films, adhesives, paints, etc., specifically printed wiring boards, flexible wiring boards, surface protection films or interlayer insulation films for semiconductor integrated circuit elements, coating materials for enameled electric wires, various laminates, Useful for gaskets, etc.

[Brief explanation of drawings]

FIG. 1, FIG. 2, and FIG. 3 are diagrams showing infrared absorption spectra of polyamic acid compounds obtained in Examples of the present invention, respectively.

Claims (1)

[Scope of Claims] 1 A structure obtained by removing two hydroxyl groups from 2,3,5-tricarboxy-cyclopentane-acetic acid, and one hydrogen from each of two amino groups of an aliphatic or alicyclic diamine. Structural unit 30 ~ in which the structure excluding atoms is bonded through an amide bond
100 mol% and a structural unit obtained by dehydration and ring closure of at least one of the amide bonds of the structural unit 0-
A polyamide acid compound consisting of 70 mol% of repeating structural units and having an intrinsic viscosity [η] (30°C, in N-methyl-2-pyrrolidone solvent) of 0.05 to 5 dl/g.