JPH03255067A - Fluorine-containing bismaleimide and its production - Google Patents

Abstract

NEW MATERIAL:2,2-Bis(3-maleimido-4-methylphenyl)hexafluoropropane expressed by formula I. USE:Useful as an intermediate for polymers. Cured products obtained by reacting the compound expressed by formula l with an amine-terminated oligomer have characteristics such as a low dielectric constant and dielectric loss further with flexibility and are excellent also in heat resistance. PREPARATION:A fluorine-containing diamine expressed by formula II is made to react with maleic anhydride to initially provide a bismaleamic acid expressed by formula III, which is then cyclodehydrated in the second stage to form imide rings and afford the compound expressed by formula I. The dehydration is carried out in the coexistence of an acid catalyst such as p-toluenesulfonic acid in an amount of 0.01-0.5mol based on 1mol amic acid group by heating at 50-200 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Industrial Field of Application The present invention relates to a novel fluorine-containing bismaleimide useful as a polymer intermediate and a method for using 9jL thereof.

(b) Conventional technology In recent years, as type equipment and electronic equipment have become larger in capacity, smaller and lighter, more reliable, and more dense, materials that are used in these devices are becoming more heat resistant and flexible. Organic materials are required.

Conventionally, polyamino bismaleimide (e.g.,
A polyimide resin consisting of N,N"-diphenylmethane bismaleimide and 4.4"-diaminodi7enylmethane described in Japanese Patent No. 3250 has been used.

4. Problems to be solved by the invention However, - the cured product of the resin described above has poor heat resistance, flexibility,
There was a problem with the deterioration of dielectric properties at high temperatures.

In particular, with the recent development of large-sized computers, there is a demand for higher Shinchin transmission speeds in computers.As is clear from the following equation, lowering the dielectric constant of the substrate is an essential issue in order to increase this speed. It becomes.

Under these circumstances, polyimide resins and fluororesins are attracting attention because of their excellent heat resistance, visibility, and electrical properties.

However, in the former board, the dielectric current is still I M
At the frequency of T (7), the dielectric constant is high at 4 or more, and the dielectric constant of the latter substrate is about 2.5, which shows satisfactory characteristics, but the processability and dimensional stability, especially the multilayer circuit board when fabricating it, is high. It has the disadvantage of extremely poor dimensional stability under high temperature conditions in the chemical process.

In response, the present inventors have proposed a thermosetting composition comprising a terminal amine imide oligomer and a polymerimide as described in Japanese Patent Application No. Hei J-227750. This composition is selected for its heat resistance and visibility, and has low dielectric properties.

However, since this thermosetting composite contains polymaleimide in polyimide oligomer, its dielectric properties are slightly lower than that of polyimide alone.

Therefore, the inventors of the present invention have conducted extensive studies in order to achieve better heat resistance, through-hole adhesion reliability, and dimensional stability, as well as lower dielectric properties.
) It has been discovered that the fluorine-containing bismaleimide represented by the following formula can be incorporated into specific terminal amine oligomers, and the polymers can be heated and cured.

An object of the present invention is to provide a novel fluorine-containing bismaleimide that can be suitably used in L resin introduction products and can further improve the dielectric properties of the cured product by using one of them.

(d) Means to solve the problem The fluorine-containing bismaleimide of claim 1 has the formula N)- 4- C.F.

It is characterized by being expressed as.

Furthermore, the invention of claim 2 relates to a method for producing a fluorine-containing bismaleimide represented by the above formula (1), and is a method for producing a fluorine-containing bismaleimide represented by the formula (IT) CF.

It is characterized by reacting a fluorine-containing diamine represented by the formula with maleic anhydride.

The fluorine-containing bismaleimide represented by description (I) can be synthesized from 2,2-bis(3-amino/-4-methyl7enyl)hexafluoropropane and maleic anhydride.

The synthesis method is not particularly limited, and example 1! 'In the first step, bismaleamic acid represented by formula (III) is synthesized.

This reaction is advantageously carried out using a solvent in which the two raw materials are brought into contact. Commonly used solvents include N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, N-methylcaprolactam, tetrahydro7rane, dioxane, acetone, diethylketone, etc. can.

Next, in the second step, the maleamic acid obtained above is dehydrated and cyclized to generate an imide ring. For this reaction, a known method described, for example, in JP-A No. 60-260623 may be used. That is, in dehydrating bismaleamic acid represented by formula N11), p
-) The desired reaction can be achieved by heating an acid catalyst such as luenesulfonic acid or benzenesulfonic acid to 6-50 to 200°C in the presence of 0.01 to 0.5 mol per 1 mol of amic acid group. .

The fluorine-containing bismaleimide represented by the formula (1) of the present invention is -Kanzo (IV) (where a is an integer of 1 or more, Ar is represented by the general formula (V), and the -Kanzo (IV) In V), Rf is at least one selected from a perfluoroalkyl group, X and Y are the same or different alkyl groups, and a 7-alkyl group, and n is 0 or 1. m is 0 to 4; integer, (h5fO
It is an integer of ~4. ) to form a thermosetting resin having low dielectric constant, low dielectric loss, heat resistance, and flexibility.

(e) Effect The fluorine-containing bismaleimide of the present invention has the above structure,
This fluorine-containing bismaleimide is reacted with the terminal amine oligomer represented by the general formula (■), and the cured product obtained has further improved properties such as low dielectric constant and low dielectric loss, and has flexibility when rolled. Moreover, it has excellent heat resistance.

The detailed reason for this is not clear, but by introducing fluorine atoms into the molecule and increasing the fluorine content in the molecule,
It is understood that the electronic polarizability due to the C--F bond decreases, which causes the dielectric constant to increase f.

In addition, the cured product obtained in this way has a specific repeating unit in the molecular main chain, and the zigzag structure of this repeating unit provides excellent flexibility, and it is also possible to introduce fluorine atoms into the molecule. It is understood that this weakens the phase budding effect between molecules and improves flexibility from these points.

Furthermore, the fluorine atom is larger than the hydrogen atom, and steric hindrance occurs when the fluorine atom enters the molecule, which is thought to strengthen the three-dimensional crosslinked structure of the polymer and improve its heat resistance. .

7-(n Examples The present invention will be described in detail based on Examples below, but the present invention is not limited to these.

Example 1 Maleic anhydride 1 0.7 9 [1 (0.1 1 m
of) was dissolved in 180 g of toluene. To this, 2t2
-bis(3-ami7-4-methylphenyl>hexafluoropropane 18,12g (0.05mof
) to N-methylpyrrolidone 701? was added dropwise as a solution and allowed to react at room temperature for 1 hour. Additionally, p-)luenesulfonic acid hydrate 0. 4 8g (0.0 0 2 5
After adding moZ), the mixture was heated to reflux and reacted for 5 hours while separating water distilled out from toluene.

After the reaction, the reaction solution was poured into a large amount of water, and the precipitated solid was collected by filtration and dried to obtain 2,2-bis(3-maleimido-4-methylphenyl)hexafluoropropane 2.
6.0g was obtained. A pure compound was obtained by recrystallizing this from chloroform.

As shown in the first flash, this infrared absorption spectrum shows j-720cm-' and 1. 7 7 0cm -'
It was confirmed that this was the target compound because a characteristic absorption similar to that of white rice appeared on the imide bond.

Application example 1 20.8 g of 2,2-bis(3.4-dicarboxyphenyl)hexafluoropropane dihydrate in a flask
(0.047moN), 2.2-bis(4-
(4-Amino7eth/xy)phenyl1hexafluoropropane (BAPF)2 7. 4 6g (0.0
5 3mo12), N-methyl-2-pyrrolidone (N
MP) 1 1 2.79g was prepared, and in a nitrogen stream, 30
Stirring was carried out for 12 hours at a temperature below ℃, and the solid content concentration was 30.
．． An amic acid oligomer with 0% by weight of terminal amine was obtained (
Intrinsic viscosity 0.29 g/dl).

Next, this amic acid solution was stirred at 145°C for 2 hours, then at 150°C for 3 hours, and then at 160°C for 2 hours to perform dehydration, ring closure, and imidization to obtain an imide oligomer with a terminal amine. 0.25 g/cH', and this imide oligomer solution contained 0.011 m of amide 7 groups.
ol! It contained.

2 obtained in Example 1 to the obtained imide oligomer solution.
, 2-bis(3-maleimido-4-methylphenyl)hexafluoropropane 23.32. (0045mob)
and N-methyl-2-pyrrolidone (NMP) 3i28 were added thereto, followed by stirring in the dark at 160°C for 3 hours and then at 180°C for 100 minutes to form a prepolymer. This solution was cast on a glass plate and heated to 100°C for 4 hours and 220°C for 14 hours.
The film was heated at 260° C. for 5 hours and finally at 300° C. for 1 hour to obtain a film with a thickness of 80 μIn. The glass transition temperature of this film was 270°C, and the 5% weight loss hot water temperature was 471°C. In addition, the dielectric constant and dielectric weight tangent are 2,
74 (1, MHz), 0. O017(i MH
7,).

Application examples 2 to 6 Using each of the siamin shown in Table 1, the amount used was
A film was produced in the same manner as in Example 1 except as shown in the table.

Table 1 shows the results of each of those characteristics.

Comparative Examples 1 to 3 Same as Example 1 except that the bismaleimides of BA and PF were used as the bismaleimides, and the diamines shown in Table 1 were used, and the amounts used of each were as shown in Table 1. A film was produced in the same manner.

The W property results are shown in Table 1.

(Left below) As is clear from Table 1, the thermosetting resin using the fluorine-containing bismaleimide of Example 1 of the present invention has particularly good dielectric properties compared to the case of using the bismaleimide shown in the comparative example. It is recognized that the company is superior in terms of

(g) Effect of the invention The fluorine-containing bismaleimide of the present invention has a specific structure containing a fluorine atom in the molecule, and this fluorine-containing bismaleimide reacts with the terminal amine oligomer represented by the general formula (IV). The obtained cured product has excellent properties such as low dielectric constant and low dielectric loss, is flexible, and has excellent heat resistance.

Further, according to the production method of the present invention, the fluorine-containing bismaleimide of the present invention can be obtained efficiently and easily without using special techniques or special equipment.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum of the fluorine-containing bismaleimide of the present invention.

Claims (2)

[Claims] (1) Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼…(I) A fluorine-containing bismaleimide represented by (2) The fluorine-containing bismaleimide according to claim 1, characterized in that the fluorine-containing diamine represented by formula (II) ▲ includes mathematical formulas, chemical formulas, tables, etc. ▼...(II) and maleic anhydride are reacted. manufacturing method.