JP2631899B2 - Resin composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a resin composition comprising aromatic polysulfone and aromatic polyimide having excellent heat resistance, team resistance, dimensional stability, mechanical strength and the like, and a resin composition comprising the same. It relates to a manufacturing method.

[Conventional technology]

Heretofore, certain aromatic polysulfones have been successfully obtained with a high degree of polymerization, such as thermal stability at about 200 ° C., mechanical properties such as tensile strength and bending strength, X-ray, β-ray, and the like.
A product having excellent steam resistance such as radiation resistance to rays and γ rays and dimensional stability in steam is sold by ICI under the trade name Victrex, for example.

However, these resins exhibit excellent resistance to aliphatic hydrocarbons, alcohols, gasoline, or some aromatic solvents, but certain organic solvents, such as ketones,
Ester, halogenated hydrocarbons and the like have a difficulty in showing solubility.

On the other hand, aromatic polyimide obtained by the reaction of aromatic diamine and tetracarboxylic dianhydride has higher heat resistance than aromatic polysulfone, as well as mechanical properties, dimensional stability, flame retardancy, electrical insulation, Because of its excellent chemical properties, it is widely used in the fields of electric / electronic equipment, aerospace equipment, etc., and Kapton developed by DuPont is a representative aromatic polyimide.

However, aromatic polyimides with excellent heat resistance are generally inferior in processability or have a problem in steam resistance, and resins developed for improving processability are inferior in heat resistance and chemical resistance. There were difficulties.

As described above, aromatic polysulfone and aromatic polyimide each have excellent surfaces, but at high temperatures and in a steam atmosphere, in an environment where various solvents are handled, etc.
It was not possible to use either alone.

[Problems to be solved by the invention]

Therefore, a composition in which these two resins are intimately mixed,
It is conceivable that the resin will have good physical properties unique to each resin.

However, these two types of resins are not uniformly mixed even if they are melt-mixed, separate to form independent phases, and the expected physical properties cannot be obtained.

As a mixing method using a solvent, a method using polyamic acid, which is a precursor of aromatic polysulfone and aromatic polyimide, can be considered.

However, even with this method, a uniform composition cannot be obtained as in the case of the above-mentioned melting method.

In recent years, IPNs (Interpenetrating Polymer Netwo
rks) is gaining attention.

According to this method, a composition more uniformly dispersed can be obtained by synthesizing another polymer in the presence of one polymer.

However, this method is also not applicable to all combinations of polymers, and does not provide a solution for obtaining a uniform composition comprising the aromatic polysulfone and the aromatic polyimide of the present invention.

The present invention solves the above-mentioned problems, and a homogeneous mixture of aromatic polysulfone and aromatic polyimide, that is, excellent heat resistance, steam resistance, chemical resistance, workability, mechanical strength, and the like. It is an object of the present invention to provide a resin composition and a method for producing the composition.

[Means for solving the problem]

The present inventors have conducted intensive studies to achieve the above object, and as a result, in an organic solvent and in the presence of aromatic polysulfone, while irradiating ultrasonic waves, by synthesizing an aromatic polyimide, It has been found that a uniformly mixed resin composition can be obtained, and the present invention has been completed.

That is, the present invention provides (1) a mixture containing an aromatic polysulfone and an aromatic polyimide obtained by the following method (2) or (3),
A resin composition comprising an intimate mixture of aromatic polysulfone and aromatic polyimide in an amount of 10 to 70% by weight and aromatic polyimide of 30 to 90% by weight based on the total amount of aromatic polysulfone and aromatic polyimide, (2) A resin characterized by reacting an aromatic diamine and an aromatic tetracarboxylic dianhydride in an organic solvent and in the presence of an aromatic polysulfone while irradiating ultrasonic waves having a frequency of 20 KHz to 3 MHz. And (3) in an organic solvent, a compound represented by the general formula: In the presence of an aromatic polysulfone having a repeating unit represented by the following formula, an aromatic compound represented by the following general formula: H ₂ N—Ar—NH ₂ (wherein, Ar is a divalent aromatic group) Diamine and general formula (Wherein, R is a tetravalent group selected from the group consisting of a monocyclic aromatic group, a non-condensed polycyclic aromatic group in which condensed polycyclic aromatic groups are connected to each other directly or by a bridge member. The aromatic tetracarboxylic dianhydride represented by the formula
The gist of the present invention is a method for producing a resin composition, which comprises reacting while irradiating ultrasonic waves of 20 KHz to 3 MHz.

The aromatic polysulfone used in the present invention is a polyarylene compound in which an arylene unit is randomly or regularly located together with an ether and a sulfone bond, and has an intrinsic viscosity (0.5 g / dl, dimethylformamide, 30 ° C.) of about 0.1 to 4.
A value of 0, preferably about 0.3 to 2.0 is suitable.

(In the formula, Z is a divalent alkylene group or carbonyl group, or an oxygen atom, and m and n are 0 or 1.) As a more specific example of the repeating unit, And the like.

Examples of the aromatic diamine represented by the general formula (I) which can be used within a range that does not impair various good physical properties of the polyimide resin used in the present invention include metaphenylenediamine, orthophenylenediamine, and aminobenzylamine. , P-aminobenzylamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,
3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, bis [4- (3-aminophenoxy) phenyl] methane,
Bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4-
(4-aminophenoxy] phenyl] propane, 2,2-
Bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1 , 1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 3-bis (3-aminophenoxy) benzene, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis- [4-
(3-aminophenoxy) phenyl] ketone, bis [4
-(4-aminophenoxy) phenyl] ketone, bis-
[4- (3-aminophenoxy) phenyl] sulfone,
Bis- [4- (4-aminophenoxy) phenyl] sulfone, bis- [4- (3-aminophenoxy) phenyl] ether, bis- [4- (4-aminophenoxy)
Phenyl] ether, 1,4-bis- [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis- [4
-(3-aminophenoxy) benzoyl]] benzene and the like.

In the present invention, examples of the aromatic tetracarboxylic dianhydride represented by the general formula (II) that can be reacted with the aromatic diamine as described above include pyromellitic dianhydride, 3,3 ′,
4,4'-benzophenonetetracarboxylic dianhydride, 2,
2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride Product, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl)
Ether dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride Compound, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,
3,6,7-anthracenetetracarboxylic dianhydride, 1,2,
7,8, -phenanthrenetetracarboxylic dianhydride and the like can be mentioned.

On the other hand, as an organic solvent that dissolves both aromatic polysulfone and aromatic polyamic acid generated from aromatic diamine and aromatic tetracarboxylic dianhydride, amide solvents, ether solvents, phenol solvents and the like are used. Specifically, N, N-dimethylformamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2 -Dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran, 1,3
-Dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide, dimethyl sulfone, tetramethylurea, hexamethylphosphoramide, phenol, m-cresol, p-cresol, o-cresol, anisole, p-chlorophenol, Hexafluoroisopropyl alcohol and the like can be mentioned.

These organic solvents can be used alone or in combination of two or more.

A homogeneous resin composition comprising an aromatic polysulfone and an aromatic polyimide according to the present invention is obtained by dissolving an aromatic polysulfone and an aromatic diamine in an organic solvent, and irradiating the solution with an ultrasonic wave while irradiating an aromatic tetrasulfone and an aromatic diamine. It can be obtained by injecting a carboxylic dianhydride and reacting the aromatic diamine with the aromatic tetracarboxylic dianhydride.

That is, an aromatic polysulfone having a repeating unit represented by the general formula (III) and an aromatic diamine represented by the general formula (I) are dissolved in an organic solvent, and the resulting solution is preferably at about -30 ° C to 100 ° C. Is to maintain the temperature of about -20 ° C to 50 ° C, and react the aromatic tetracarboxylic dianhydride represented by the general formula (II) for about 1 hour to 24 hours under ultrasonic irradiation. As a result, a uniform resin composition containing a repeating unit represented by the general formula (III) and the following general formula (IV) can be obtained.

(R in the formula (IV) is the same as R in the formula (II);
Is a divalent aromatic group. Holding the above solution at about −30 ° C. to 100 ° C. may cause the melt to solidify below about −30 ° C.
If it exceeds 300, it depends on the boiling point of the organic solvent used, but the vapor pressure increases, which is not preferable in terms of the reaction.

In addition, the ultrasonic irradiation condition is a frequency of about 20 KHz to 3 MHz.
z, preferably about 30 KHz to 500 KHz. Frequency is about 20
If the frequency is lower than KHz, there is a possibility that the uniformly mixed molecules may be destroyed. If the frequency is higher than about 3 MHz, there is little effect on the uniform mixing.

Ultrasonic irradiation can be performed continuously from the time when the aromatic polysulfone and the aromatic diamine are dissolved in the organic solvent.

The resin obtained above is precipitated in a solvent such as methanol and dissolved in an organic solvent again, or the reaction solution is kept for about 1 to 24 hours at a temperature of about 100 ° C.
To 300 ° C., preferably from about 120 ° C. to 250 ° C., to obtain a uniform target resin composition containing a repeating unit represented by the general formula (III) and the following general formula (V). Can be

The high temperature treatment at this time is mainly intended to form polyimide by ring closure of polyamic acid. (R and Ar in the formula (V) are the same as those in the formula (IV).) In the resin composition of the present invention, within a range that does not impair the purpose of the present invention, about 10 wt ppm to several wt%. , Antioxidants, heat stabilizers, UV absorbers, flame retardant aids,
One or more ordinary additives such as an antistatic agent, a lubricant, and a coloring agent can be added.

Thermoplastic resins such as polyimide, polycarbonate, polyacrylate, polyamide imide, and polyether imide; thermosetting resins such as phenolic resin and epoxy resin; clay, mica, silica, graphite, glass beads, alumina, calcium carbonate, Glass fiber,
Fillers such as carbon fiber and reinforcing agents can be added in an appropriate amount from several weight% to several tens weight% depending on the purpose.

[Action]

In the resin composition of the present invention, the aromatic polysulfone and the aromatic polyimide are intimately mixed, and become a resin having the properties of the aromatic polysulfone and the properties of the aromatic polyimide. In addition to being able to be formed well by a known forming method such as a spinning method and a rotational forming method, it can be used well as a coating material as a solution, and is excellent in film forming properties.

At this time, about 10 to 70% by weight of the aromatic polysulfone based on the total amount of the aromatic polysulfone and the aromatic polyimide,
The reason why the amount of the aromatic polyimide is set to about 30 to 90% by weight is to effectively obtain the above-mentioned action.

That is, the aromatic polysulfone exceeds about 70% by weight,
When the amount of the aromatic polyimide is less than about 30% by weight, the intimate mixing as described above is not performed, phase separation is remarkable, the uniformity of the resin composition of the present invention when formed into a film is poor, and the high-temperature corrosion resistance is low. And the mechanical strength becomes insufficient. On the other hand, aromatic polysulfone is less than about 10% by weight, and aromatic polyimide is about
If it exceeds 90% by weight, steam resistance and elasticity become insufficient. Therefore, about 10 to 70% by weight of aromatic polysulfone
Thus, when the amount of the aromatic polyimide is about 30 to 90% by weight, a resin composition having balanced properties while maintaining excellent properties of both resins is obtained.

Further, in the production method of the present invention, in an organic solvent solution of aromatic polysulfonic acid, by reacting aromatic diamine and aromatic tetracarboxylic dianhydride to synthesize aromatic polyimide, aromatic polysulfonic acid and This is to obtain a resin composition of the present invention in which an aromatic polyimide is intimately mixed.

Then, in a series of steps of this method, or at the time of high-temperature treatment mainly aimed at the formation of polyimide by ring closure of the above-mentioned polyamic acid, ultrasonic waves are irradiated,
The irradiation of the ultrasonic wave has an effect of making the processing temperature during the series of steps and the formation of the polyimide lower than that in the case where no ultrasonic wave is irradiated.

For example, by irradiating an ultrasonic wave at the time of forming the above-mentioned polyimide, it can be easily imidized even at a low temperature treatment, and its characteristics can be brought out. In other words, the characteristics obtained by a process requiring a high temperature of, for example, about 300 ° C. without irradiation with ultrasonic waves can be obtained by a low-temperature process of about 150 ° C.

In addition, in order to enable low-temperature treatment without using ultrasonic irradiation, it is conceivable to use an imidizing agent.However, when the imidizing agent remains, the imidizing agent may adversely affect the physical properties of the resin. Absent. For example, imidazole-based compounds known as catalysts for imidizing agents are likely to remain in the resin after molding, depending on the amount of addition, and when molded into a film or the like, their mechanical strength is impaired. is there.

〔Example〕

Example 1 A 50 ml three-necked flask equipped with a stirrer and a nitrogen inlet tube was used as a basic structure. Aromatic polysulfone (grade 5003 manufactured by ICI)
P) 0.40 g, 1.03 g of 4,4'-diaminodiphenyl ether,
20 ml of dimethylacetamide was taken, placed in an ultrasonic reaction vessel having a transmission capability of 40 KHz, and stirred at 0 ° C. under a nitrogen atmosphere under ultrasonic irradiation until completely dissolved.

In this example, an ultrasonic reaction tank was used for ultrasonic irradiation. However, it is also possible to apply the tip of a probe-type ultrasonic generator to another port of a flask or into a reaction solution for irradiation.

After complete dissolution, under ultrasonic irradiation, slowly add 1.13 g of pyromellitic dianhydride while paying attention to the temperature rise, and adjust the temperature to about 0 ° C for 100 r.
Stirred at pm for 4 hours.

After completion of the reaction, the pale yellow transparent viscous reaction solution was immediately spread on a glass plate, and the temperature of the film was gradually increased under reduced pressure, and the film was heated at 150 ° C. for 15 hours to form a yellow transparent smooth film. Obtained.

Further, a part of this film was subjected to heat treatment at 300 ° C. for 6 hours under reduced pressure to obtain films having different treatment temperatures.

To know the mechanical properties of these films, elongation,
The tensile strength and the initial elastic modulus were measured.

For measurement, the measurement sample part was 50 μm thick, 50 mm long and 10 mm wide.
And the tensile speed was 5.0 mm / min.

Table 1 shows these values and the respective physical property values of the aromatic polyimide of the aromatic polysulfone as a reference example.

The results of film forming properties on a glass plate are also shown.

Example 2 In order to produce resin compositions having different mixing ratios of aromatic polysulfone and aromatic polyimide, 1.19 g of aromatic polysulfone and 1.00 of 4,4′-diaminodiphenyl ether were used.
g, pyromellitic dianhydride was changed to 1.09 g, and the reaction was carried out in the same manner as in Example 1 to obtain a yellow, transparent, smooth film. Was measured.

 The results are shown in Table 1.

Comparative Examples 1 and 2 Except not irradiating ultrasonic waves, the reaction was carried out in the same manner as in Examples 1 and 2, and various physical properties of the obtained film were measured in the same manner as in Examples 1 and 2. Are also shown in Table 1.

The amounts of each component in Comparative Example 1 are the same as in Example 1, and the amounts of each component in Comparative Example 2 are the same as in Example 2.

Example 3 0.40 g of the same aromatic polysulfone as in Example 1, 4.4'-
The reaction was carried out in the same manner as in Example 1, except that 1.03 g of diaminodiphenyl ether and 1.67 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride were used as the aromatic tetracarboxylic dianhydride. The physical properties of the obtained film were measured in the same manner as in Example 1. Table 2 shows the results.

Example 4 1.22 g of the same aromatic polysulfone as in Example 1, 4,4'-
The reaction was carried out in the same manner as in Example 1, except that 1.02 g of diaminodiphenyl ether and 1.64 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride were used as the aromatic tetracarboxylic dianhydride. The physical properties of the obtained film were measured in the same manner as in Example 1. The results are shown in Table 2.

Example 5 1.76 g of the same aromatic polysulfone as in Example 1, 4,4'-
The reaction was carried out in the same manner as in Example 1, except that 0.51 g of diaminodiphenyl ether and 0.82 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride were used as the aromatic tetracarboxylic dianhydride. The physical properties of the obtained film were measured in the same manner as in Example 1. The results are shown in Table 2.

Comparative Examples 3, 4, 5 Except for not irradiating the ultrasonic waves, the reaction was performed in the same manner as in Examples 3, 4, and 5, and the obtained films were subjected to Examples 3, 4, and 5.
Various physical properties were measured in the same manner as in 5, and the results are shown in Table 2.

The amount of each component in Comparative Example 3 was Example 3, the amount of each component in Comparative Example 4 was Example 4, and the amount of each component in Comparative Example 5 was Example 5.
Is the same as

Example 6 1.21 g of the same aromatic polysulfone as in Example 1, 4,4'-
The reaction was carried out in the same manner as in Example 1, except that 1.04 g of diaminodiphenyl ether and 1.53 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride were used as the aromatic tetracarboxylic dianhydride. The physical properties of the obtained film were measured in the same manner as in Example 1.

Table 3 shows the results together with the respective physical property values of the aromatic polyimide as a reference example.

Comparative Example 6 A reaction was carried out in the same manner as in Example 6, except that no ultrasonic wave was applied. The obtained film was measured for various physical properties in the same manner as in Example 6, and the results are shown in Table 3. Show.

Example 7 As a basic structure Reaction in the same manner as in Example 1 using 2.21 g of an aromatic polysulfone having the following formula: 1.00 g of 4,4'-diaminodiphenyl ether, 1.61 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride Was carried out to obtain a yellow transparent smooth film, and various physical properties of this film were measured in the same manner as in Example 1. The results are shown in Table 4.

Comparative Example 7 A reaction was carried out in the same manner as in Example 7 except that no ultrasonic wave was applied, and various physical properties of the obtained film were measured in the same manner as in Example 7. The results are shown in Table 4. Show.

[Effects of the Invention] As described above in detail, the resin composition of the present invention comprises the aromatic polysulfone represented by the general formula (III) and the general formula (V)
Because it is an intimate mixture with an aromatic polyimide represented by the formula, it has the properties of aromatic polysulfone and aromatic polyimide, and has properties such as heat resistance, steam resistance, chemical resistance, mechanical strength, and electrical properties. It is an excellent industrial material that is excellent, has excellent processability and flexibility, and is excellent in moldability and film formability.

Therefore, the resin composition of the present invention is used for electric and electronic devices,
It can be used in various fields for transportation equipment, plant maintenance, and other general industrial equipment.

In addition, the method for producing the resin composition of the present invention allows the conventional hardly compatible resin to be intimately mixed with a high molecular weight, enables low-temperature treatment during imidization, and requires conventional high-temperature treatment. It solves difficulties during coating and has high industrial value.

 ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Ikue Kaneda 5-30-12-704, Ogikubo, Suginami-ku, Tokyo (56) References JP-A-59-122547 (JP, A) JP-A-63-304057 JP, A) JP-A-62-174230 (JP, A) JP-A-2-199176 (JP, A)

Claims (3)

(57) [Claims] An aromatic diamine and an aromatic tetracarboxylic dianhydride are reacted in an organic solvent and in the presence of aromatic polysulfone while irradiating ultrasonic waves having a frequency of 20 KHz to 3 MHz. A method for producing a resin composition. 2. A compound represented by the general formula: In the presence of an aromatic polysulfone having a repeating unit represented by the general formula: H ₂ N—Ar—NH ₂ (1) (wherein, Ar is a divalent aromatic group) Aromatic diamine and a general formula (Wherein, R is a tetravalent group selected from the group consisting of a monocyclic aromatic group, a non-condensed polycyclic aromatic group in which condensed polycyclic aromatic groups are connected to each other directly or by a bridge member. The aromatic tetracarboxylic dianhydride represented by the formula
A method for producing a resin composition, comprising reacting while irradiating ultrasonic waves of 20 KHz to 3 MHz. 3. A mixture containing an aromatic polysulfone and an aromatic polyimide obtained by the method (1) or (2), wherein the amount of the aromatic polysulfone is 10 to 10 with respect to the total amount of the aromatic polysulfone and the aromatic polyimide. A resin composition comprising 70% by weight of an intimate mixture of 30 to 90% by weight of an aromatic polyimide.