JPH03220234A - Thermosetting resin molding - Google Patents

Abstract

PURPOSE:To obtain the title molding having excellent heat resistance, solvent resistance and processability, high electric resistance and low permittivity by molding a specified fluorinated polyazomethine and heat treating the molding. CONSTITUTION:A fluorinated polyazomethine mainly consisting of repeating units of the formula (wherein Ar1 and Ar2 are bivalent aromatic groups, and at least one of them contains a perfluoroalkylene group and/or a fluorinated aromatic group) is molded, and the molding is heat treated.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Industrial Field of Application The present invention relates to a thermosetting resin molded article having excellent heat resistance, solvent resistance, workability, and moldability.

(b) Prior Art Polyazomethine polymers usually have poor solubility in solvents, and are therefore only soluble in special solvents, which limits their production methods and, therefore, limits their uses.

Polyazomethine can be obtained, for example, by the melt polymerization method, but since the polymerization and molding are carried out in a molten state, the monomers and polymers may thermally decompose or unreacted monomers may remain, which adversely affects the properties of the molded product. I often see it.

For this reason, a thermosetting resin molded article made of polyazomethine, which will be described below, has been proposed.

That is, in reacting tele7taraldehyde, 3,4-diaminodiphenyl ether, and p7z nylene diamine derivative at a predetermined blending ratio as main raw materials, a predetermined noamine component of 1 is mixed with, for example, N-methylpyrrolidone (NMP ), is dissolved in hexamethylphosphortriacetate (HMPA), difludehyde as one raw material is added as 's81, and reacted to obtain a polycondensate (polymer).

In this case, metal oxides such as lithium chloride, calcium chloride, etc. are added for solubilization.
3-234030).

(c) Problems to be Solved by the Invention However, impurities such as metal ions remain in the molded product obtained in this way, which has a particularly negative effect on electrical properties, so its use is extremely limited.

4. In general, thermosetting resins such as epoxy resins are often used as insulating materials for electrical and electronic equipment, printed wiring boards, and laminates. Electrical properties may deteriorate due to the presence of
There are problems such as corrosion of the electrodes of electrical/electronic equipment and printed wiring boards, etc. Therefore, the actual situation is that poly-7zomethine is not put into practical use even though it has excellent heat resistance.

Furthermore, recently, fluorine-containing polyimide has attracted attention as a low dielectric constant material. For example, an object of the present invention is to provide a method for producing a molded product such as S 1xef.

(d) Means for Solving Problem 111 In order to achieve the above object, the thermosetting resin molded product of the present invention uses solvent-soluble polyazomethine having a specific composition, and after molding, Heat treated to make an insoluble and infusible molded product,
It is possible to obtain products with excellent heat resistance, solvent resistance, reduced coefficient of linear thermal expansion, and low dielectricity.

That is, although the thermosetting resin molded article of the present invention is known to have the general formula (I), it has a fatal drawback that it cannot be used in the electrical and electronic fields because it is soluble in solvents.

The present invention has been made in view of the above circumstances, and is required in cutting-edge fields to not only improve formability and workability, but also to improve heat resistance, solvent resistance, lower wire tensile coefficient, and lower dielectric strength. CH=
It is formed by molding and heat-treating a fluorine-containing polyazomethine mainly having repeating units represented by N Arz N +---(E ).

(However, Arl and Ar2 represent divalent aromatic groups, and A
fluorine-containing polyazomethine represented by the general formula (1) t'; is a solvent, such as N-methyl-2-pyrrolidone (NM
P), dimethyl sulfoxide (DMSO), N
.

Aprotic polar solvents such as N-tumethyl 7cetamide (DMAc), N,N-nonitylacetamide (DEAC), N,N-tumethylformamide (DMF), and general-purpose solvents such as toluene and xylene depending on the composition. It is also soluble in non-polar solvents.

This fluorine-containing polyazomethine can be obtained by solution polycondensation reaction of approximately equimolar amounts of the corresponding dialdehyde and diamine. Although this heptadium-containing polyazomethine can be obtained by bulk melt polycondensation of approximately equal moles of the corresponding dialdehyde and diamine, according to the present invention, it can be obtained in the same amount by solution polymerization. In this case, it is preferable to remove the water produced by azeotropy,
Since the properties can be improved by the heat treatment described later, it is not necessary to remove the produced water.

Specifically, the fluorine-containing polyazomethine described in item 7 is ordinary poly 7
91 in the same manner as zomenane and its copolymers.

That is, polyazomethine and its copolymers can be thermally polymerized from suitable monomers, preferably under anhydrous conditions in an inert atmosphere.
N A r2 N H2) and dialdehydes or their derivatives, diacetals, diketones, etc. [(Z , 0 )
Equimolar amounts of 2HCA r+c H(OZ 2)2 are reacted together in a reaction vessel. In this case, an inert gas (N
While introducing a predetermined amount of dehydrated solvent (e.g. NMP, DMAc, etc.)
~40%) and stirred at room temperature for several hours.

Next, in order to remove byproducts (water, methanol, etc.), the mixture is heated for several hours to several tens of hours, and a solvent such as benzene is added for dehydration, for example, by Dean-Stark's azeotropic dehydration method. As polymerization progresses, the viscosity of the solution increases. As the polymerization progresses and the solution viscosity increases, handling becomes troublesome, so in order to increase the amount of solvent or to adjust the degree of polymerization, a chain terminator may be added during polymerization to increase the amount of solvent or to adjust the degree of polymerization.

Examples of the terminal capping agent and chain terminator include 7niline, 4-carpoxybenzaldehyde, and 4-7minoacetanilide.

The obtained polymer solution is desolventized (heated hot air, etc.)
and can be molded. Alternatively, the obtained polymer solution may be poured into a non-solvent such as water or methanol to precipitate the polymer, and then the polymer may be collected, washed, dried, and then molded. .

In the above general formula (I), Ar+ represents a divalent aromatic group, for example, ]C elbow, 10. '-0-1z so -1・tsu'',=CH
2=:14 so CF.

Examples include.

However, in the present invention, it is an essential component that at least one of the above-mentioned Ar+ or Ar2 groups contains a perfluorofluorylene group or a heptadated aromatic group.

For example, Arr represents a divalent aromatic group, for example, (in the above formula,
n is an integer from 1 to 8. ), etc.

The average degree of polymerization of the fluorine-containing 7-zomethine thus obtained can be expressed as the intrinsic viscosity η (g/df), but in the present invention, this intrinsic viscosity (g/dl) is 0°1 g1d1
Above, it is particularly preferable to set it as the range of 0.15-2 g/d1. This intrinsic viscosity (g/+l) is 0.1 g/de
If it is less than 2 g/di, the effect of the heat treatment described later will be small and the film forming property will be poor. On the other hand, if it exceeds 2 g/di, the solution viscosity and melt viscosity will become extremely high, making it difficult to form. Processing becomes difficult. Moreover, when it is made into a solution, it is not preferable because it is necessary to reduce the polymer concentration and the volume change (reduction) immediately after processing becomes large and inconvenient.

Since the above-mentioned poly-7zomethine is soluble in the above-mentioned solvents, it is extremely easy to mold and process. It can be molded into fibers, films, and general resin composites.

The present invention has the most significant feature in step 7, which is heat-treated after the above-mentioned molding process.

Hereinafter, the heat treatment after molding in the present invention will be explained.

The heat treatment of the present invention is a condition under which the curdling reaction of the soluble fluorine-containing poly-7zonotine to be used occurs. - For boat fishing, heating of processed and formed fluorine-containing polyazomethine is started below the glass transition temperature, the temperature is gradually raised, and finally heat treatment is carried out above the positive transition temperature (Tg) of this polymer. (Tg + 50°C), preferably (Tg + 50°C)
g+150°C) or less.

Atmosphere × may be inert γλ such as nitrogen or in air.Also, in order to control the degree of crosslinking and coloring to some extent, an antioxidant, an oxidation promoter, silica, and 7th monium dioxide may be mixed. .

This fluorine-containing poly-7zomethine has 77 atoms in its molecular skeleton, and after molding and heat treatment, it becomes an insoluble and infusible molded product, and has excellent heat resistance, solvent resistance, and wire heat resistance. This results in a reduction in expansion coefficient and excellent low dielectric properties.

And, Art in the above general formula (I) is or 1, m is an integer of 0 to 4, l is O to 4
is an integer. ), in addition to the above characteristics,
The electrical properties, especially the dielectric constant, decrease, and the dielectric loss decreases.

Furthermore, in the above general formula (I,), a polymer is obtained in which Rf is soluble and can be cured by the above heat treatment. Furthermore, by using a specific Arl and subjecting it to the heat treatment described above, properties such as the silver S* coefficient, thermal decomposition temperature, glass 1 transition temperature, and dielectric properties are further improved.

Further, since Ar2 in the above general formula (I) is at least one selected from the following, in addition to the above-mentioned properties, the electrical properties, particularly the dielectric constant, are reduced, and the dielectric loss is reduced.

Furthermore, in the above general formula (I), since Ar2 is at least one selected from FF and F, in addition to the above-mentioned properties, the electrical properties, especially the dielectric constant, and the dielectric loss are reduced. be.

(e) Effect The present invention has the above configuration, and by introducing element 77 into the molecule, the solubility parameter (SP value) becomes small and the solubility in general-purpose solvents becomes good. Generally speaking, the relative permittivity and the SP value are in a proportional relationship, and it is understood that by introducing fluorine into the molecule, the SP value becomes smaller and the relative permittivity becomes smaller.

In addition, because the solubility in general-purpose solvents is good, it is possible to increase the degree of polymerization, which requires heat treatment, and there is less low molecular weight polymer, and the thermal properties, such as the coefficient of linear expansion, are small. , Plus (transition temperature and thermal decomposition temperature become higher, the strength of the molded product improves, flexibility is developed, and a tough molded product is obtained.

(f3 Examples The present invention will be described in detail based on Examples below, but the present invention is not limited thereto.

Example 1 Preparation of poly7zomethine solution
4 to (4-7mino7e/xy)phenyl]hexafluoropropane 0.03+soL each with a solid content of 20% by weight
N-methyl 2-pyrrolidone (N M F'
) and gradually mix the two under a nitrogen atmosphere.

After stirring overnight at room temperature, add a small amount of toluene,
The temperature was raised to 140° C., and the produced water was removed by azeotropy over about 5 hours, and then toluene was also removed to obtain an NMP'l solution of polyazomethine.

The above polyazomethine solution was uniformly applied to a heat-treated glass plate, and this was placed in a dryer at 120°C for 2 hours.
t S O℃te2i? 1111. Dry at 180°C for 5 hours. It was gradually cooled to obtain a coated 11 film (50 μm thick).

One sheet of this film was heat-treated at 230° C. for 1 hour, and one sheet of film a was heat-treated at 300° C. for 1 hour. Thermal decomposition temperature (T d), plus transition temperature (Tg), a
The tensile modulus (σ) and solvent resistance are shown in 1st R.

Examples 2 to 7 and Comparative Examples 1 and 2 Furthermore, Comparative Example 4 Various films were prepared in the same manner as in Example 1 using dialdehydes and diamines shown in Table 1.

The characteristic results are shown in Table 1.

Comparative Example 3 8 parts by weight of 3.4-diaminodiphenyl ether was added to NMP.
5.3 parts of teraldehyde was dissolved in a mixed system of 25 parts by weight, 25 parts by weight of methyl phosphorotriside, and 5 parts by weight of anhydrous lithium chloride while flowing nitrogen.
6 parts were gradually added and mixed and reacted for 48 hours at room temperature.
After the reaction was completed, the mixture was poured into water, and the precipitated yellow powder polymer was filtered off. Subsequently, washing with water was repeated, and washing with methanol and drying was performed to obtain poly7zomethine (poly-tri-a-3-7enyl ether-4'-phenylene) IJ lomethylidine-1.4-7 enylene methylidene) 112.3. I got the department.

The characteristic results are shown in Table 1.

(Left below) CHO-・TS-Cl(0(TPAL) H2N-'Q"-Nll□ (PPDΔ) From the results shown in 1st &, the dielectric constant of the example is higher than that of the comparative example. It is recognized that it has a very low coefficient of linear expansion, excellent dimensional stability, good heat resistance, and extremely high solvent resistance.

(g) Effects of the Invention In the present invention, polyazomethine has the structure described in (g) and becomes an insoluble polymer through deltaization and crosslinking by heat treatment. In addition, heat treatment can increase the plus transition temperature (
Tg) is increased, the linear expansion coefficient is decreased, dimensional stability is improved, and molded products with significantly improved heat resistance and solvent resistance can be obtained.

Furthermore, in the present invention, the molded product obtained by heat treatment has a significantly high electrical resistance and a significantly reduced dielectric constant, and as a result, it is extremely useful in the electrical and electronic fields.

Claims (5)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼……Thermosetting resin made by molding and heat-treating fluorine-containing polyazomethine that mainly has the repeating unit shown by (I) Molded object. (However, Ar_1 and Ar_2 represent divalent aromatic groups, and at least one of Ar_1 and Ar_2 contains at least one of a perfluoroalkylene group and a fluorinated aromatic group.) (2) In the thermosetting resin molded article of claim 1, Ar_1 in general formula (I) is ▲a mathematical formula, a chemical formula, a table, etc.▼, ▲a mathematical formula, a chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A thermosetting resin molded product that is at least one selected from the following. (3) In the thermosetting resin molded article of claim 1, Ar_2 in general formula (I) has a numerical formula, chemical formula, table, etc. (Rf is a perfluoroalkylene group or does not exist, and X and Y are the same) or at least one selected from different alkyl groups and fluorinated alkyl groups, where n is 0 or 1, m is an integer of 0 to 4, and l is an integer of 0 to 4. Molded object. (4) In the thermosetting resin molded article of claim 3, Rf is ▲a mathematical formula, a chemical formula, a table, etc.▼, ▲a mathematical formula, a chemical formula,
A thermosetting resin molded product that is at least one type selected from ▼, ▲Mathematical formulas, chemical formulas, tables, etc.▼ ▲Mathematical formulas, chemical formulas, tables, etc.▼ (5) In the thermosetting resin molded article of claim 1, Ar_
2. There are ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
Thermosetting resin moldings that are at least one type selected from ▼.