KR910009826B1 - Polyimide resin composition - Google Patents

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Description

Polyimide Resin Composition

The present invention relates to a molding resin composition. More specifically, the present invention relates to a polyimide molding resin composition that is excellent in heat resistance, chemical resistance, mechanical strength, and the like and excellent in molding processability.

Conventionally, polyimide has been used in the fields of electrical and electronic equipment, aerospace equipment, transportation equipment, etc., since it has excellent mechanical strength, dimensional stability, flame retardancy, and electrical insulation in addition to its high heat resistance. It is also expected to be widely used in the field where heat resistance is required.

Various polyimides having excellent properties have been developed.

However, even though it is excellent in heat resistance, it does not have a clear glass transition temperature. Therefore, when it is used as a molding material, it must be processed using a technique such as sintering molding, or it is excellent in workability, but its glass transition temperature is low and halogenated hydrocarbons are also excellent. Soluble in water and not satisfactory in terms of heat resistance and solvent resistance.

Therefore, polyimide excellent in heat resistance and solvent resistance and excellent in workability as a molding material has been desired.

As a polyimide capable of satisfying these properties, the inventors have found a polyimide composed of the following repeating units.

In the formula, x represents a benzenedicarbonyl group in which the position of two carbonyl groups in the direct, thio group, or benzene ring is meta or para, and R is an aliphatic group having 2 or more carbon atoms, a cyclic aliphatic group, or a monocyclic aromatic group. Denotes a tetravalent group selected from the group consisting of condensed polyaromatic groups, non-condensed polyaromatic groups linked directly or by a bridging member (JP-A 61-14348, 62-68817, 62-86021 and 62-50372).

The polyimide is a thermoplastic polyimide having fluidity at high temperature, in addition to excellent mechanical properties, thermal properties and electrical properties peculiar to polyimide. However, the polyimide is far superior in heat resistance and other properties as compared to conventional engineering plastics represented by polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polysulfone, polyphenylene sulfide, and the like. The moldability does not reach those resins yet.

In general injection molding and extrusion molding, the lower the viscosity at the time of melting, the better the moldability. For example, during injection molding, when the melt viscosity is high, the injection molding pressure becomes high, and excessive stress is applied to the molded article, which adversely affects the mechanical properties of the molded article. The molding cycle also becomes long. Since the polyimide of the present invention has excellent high temperature fluidity, it can be used for injection molding, but it is necessary to further improve its workability.

It is an object of the present invention to provide a polyimide resin composition for molding which is very excellent in terms of fluidity during melting without impairing the inherent properties of polyimide.

MEANS TO SOLVE THE PROBLEM The present inventors completed this invention as a result of earnestly researching in order to solve the said objective.

That is, the present invention is formula (I)

(Wherein x represents a benzenecarbonyl group in which the position of two carbonyl groups in the straight, thio group, or benzene ring is meta-position or para-position, and R is an aliphatic group having 2 or more carbon atoms, a cyclic aliphatic group, or a monocyclic aromatic group). Polyimide 99.9 and 50.0% by weight of a repeating unit of a tetravalent group selected from the group consisting of a group, a condensed polyaromatic group and an aromatic group directly or by a crosslinking group, a non-condensed polyaromatic aromatic group, and an aromatic polysulfone 0.1 It is a resin composition which consists of -50.0 weight%.

The polyimide used by this invention is a formula

Etherdiamine, ie, 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] sulfide, 1,3-bis [4- (3- Imidated polyamic acid obtained by reacting aminophenoxy) benzoyl] benzene or 1,4-bis [4- (3-aminophenoxy) benzoylbenzene with at least one tetracarboxylic dianhydride in an organic solvent You get

The tetracarboxylic dianhydride used at this time is a formula

It is tetracarboxylic dianhydride represented by.

That is, as tetracarboxylic dianhydride used, ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic acid 2 Anhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic acid Dianhydride, 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) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 4,4 '-(P-phenylenedioxy) diphthalic acid dianhydride, 4,4'-(m-phenylenedioxy) diphthalic acid dianhydride, 2,3 , 6,7-naphthalenete Lacarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride,, 1,2,3,4-benzenetetracarboxylic dianhydride, 3, 4,9,10-methylenetetracarboxylic dianhydride, 2,3,6,7-anthracenecarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride, and the like. These tetracarboxylic dianhydrides are single or 2 Mix on paper and use.

Particularly preferred tetracarboxylic dianhydrides are pyromellitic dianhydrides, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydrides, 3,3', 4,4'-benzophenonetetracarboxylic dianhydrides, bis (3 , 4-dicarboxyphenyl) ether dianhydride.

Moreover, although the polyimide used for the composition of this invention is a polyimide which uses said etherdiamine as a raw material, the polyimide obtained by mixing and using other diamine also in the range which does not impair the favorable physical property of this polyimide also It can be used in the composition of the present invention.

As diamine which can be mixed and used, for example, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, bis (3-aminophenyl) ether, (3-aminophenyl) (4-aminophenyl) ether, bis (4-aminophenyl) ether, bis (3-aminophenyl) sulfide, (3-aminophenyl) (4-aminophenyl) sulfide, bis ( 4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, bis (4-aminophenyl) sulfoxide, bis (3-aminophenyl) Sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'- Diaminobenzophenone, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4 -Aminophenoxy) phenyl] ethane, 2,2-bis [4- (4-aminophenoxy) phenylpropane, 2,2-bis [4- (4-aminophenoxy ) Phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4 ′ Bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (4- Aminophenoxy) phenyl] sulfoxide, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) Phenyl] ether, and the like.

The aromatic polysulfone used in the present invention is Well known heat resistant polymers with units are described, for example, in V, J. Leslie et al., CHEMITECH July 1975, P-426-432 and the like. In the present invention, for example, an aromatic polysulfone composed of the following repeating units is used.

As a typical aromatic polysulfone, general formula

Polyethersulfone sold under the trademark "VIC TREX PES" by British I, C, I, and / or general formula

And polysulfones sold under the trademark "UD EL POLY SULFONE" by the United Union Carbide Company.

These aromatic polysulfones can be freely produced in various polymerization degrees, and those having an appropriate melt viscosity characteristic for the desired blend can be arbitrarily selected.

The molding resin composition of the present invention is adjusted so that the polyimide 99.9 to 50% by weight and the aromatic polysulfone are in the range of 0.1 to 50% by weight.

The polyimide / aromatic polysulfone composite resin system of the present invention exhibits a significantly low melt viscosity in a high temperature region such as 350 ° C or higher. The favorable fluidization effect of the aromatic polysulfone is recognized in a small amount, and the lower limit of the composition ratio is 0.1% by weight, but preferably 0.5% by weight or more.

In addition, although the mechanical strength at high temperature of the aromatic polysulfone belongs to a superior class in the heat resistant resin, the mechanical strength, particularly the impact resistance in IZOD, is lower than that of the polyimide. Therefore, if the amount of the aromatic polysulfone in the composition is too high, It is not desirable to maintain the original mechanical strength of the mead. Therefore, the composition ratio of aromatic polysulfone has an upper limit and 50 weight% or less is preferable.

In preparing the composition according to the present invention, it can be produced by a publicly known method. For example, the following method is a preferred method.

(1) The polyimide powder and the aromatic polysulfone powder are preliminarily kneaded with a mortar, a Henschel mixer, a drum blender, a tumbler blender, a boll millibon blender or the like to obtain a powder form.

(2) The polyimide powder is first dissolved or suspended in an organic solvent, an aromatic polysulfone is added to this solution or suspension, and then uniformly dispersed, and then the solvent is removed to form a powder.

(3) After suspending the aromatic polysulfone in the organic solvent solution of the polyamic acid which is a precursor of the polyimide of the present invention, it is subjected to heat treatment at 100 to 400 ° C or using a commonly used imidating agent. After mid-ization, the solvent is removed to form a powder.

The powdered polyimide resin composition obtained as described above is used for various molding purposes as it is, that is, injection molding, compression molding, transfer molding, extrusion molding, etc., but it is more preferable to use melt blending.

Moreover, it is also a simple and effective method to melt-blend the powder of polyimide and heat resistant polymer, pellet, or powder and pellet.

As the melt blend, an apparatus used for melt blending a conventional rubber or plastic, such as a thermal roll, a Benbury mixer, a brabender, an extruder, or the like can be used. The melting temperature is set above the temperature at which the blending system is meltable and below the temperature at which the blending system starts to pyrolyze, but the temperature is usually 280 to 420 ° C, preferably 300 to 400 ° C.

As the molding method of the resin composition of the present invention, injection molding or extrusion molding, which forms a homogeneous melt blend and is a highly productive molding method, is suitable, but other transfer molding, compression molding, and sintering molding may be applied. There is no

In addition, to the resin composition of the present invention, one or more solid lubricants such as molybdenum sulfide, graphite, boron nitride, lead oxide, and lead powder may be added. In addition, reinforcing agents such as glass fibers, carbon fibers, aromatic polyamide fibers, potassium titanate fibers, and glass beads may be added.

In addition, to the resin composition of the present invention, at least one conventional additive such as an antioxidant, a heat stabilizer, a UV absorber, a flame retardant, a flame retardant aid, an antistatic agent, a lubricant, and a coloring agent is added within a range that does not impair the object of the present invention. can do.

EXAMPLE

The present invention will be described in detail through the following synthesis examples, examples and comparative examples.

Synthesis Example 1

In a reaction vessel with a stirrer, a reflux condenser and a nitrogen inlet tube, 4.0 kg (10 moles) of bis [4- (3-aminophenoxy) phenyl] sulfide and 34.8 kg of N, N-dimethylacetamide are added. 2.14 kg (9.8 moles) of pyromellitic dianhydride is added to the mixture at room temperature under a nitrogen atmosphere and stirred for approximately 20 hours at room temperature while paying attention to the temperature rise of the solution.

To the resulting polyamic acid solution, 2.02 kg (20 mol) of trimethylamine and 2.55 kg (25 mol) of acetic anhydride are added dropwise at room temperature under a nitrogen atmosphere and stirred at room temperature for about 20 hours to obtain a light yellow slurry. The slurry was filtered to obtain a light yellow polyimide powder. The polyimide powder was sludged with methanol, filtered, and dried at 180 ° C. under reduced pressure for 8 hours to obtain 5.63 kg (yield 97.5% yield) of polyimide powder. The intrinsic viscosity of the polyimide powder is 0.85 dl / g, which is dissolved in 0.5 g of polyimide powder using 100 ml of a solvent (a mixture of p-chlorophenol and phenol in a weight ratio of 90:10), This solution is measured at 35 ° C. after cooling.

Synthesis Examples 2 to 5

The same process as in Synthesis Example 1 was carried out, but the raw materials were changed as follows. In other words, various diamines are used in place of [4- (3-aminophenoxy) phenyl] sulfide, and various tetracarboxylic dianhydrides are used instead of pyromellitic dianhydrides, so that diamines, N, N-dimethylacetamides, Various polyimide powders are obtained by varying the amount of tetracarboxylic dianhydride. Table 1 shows the conditions for the synthesis of polyimide resin.

TABLE 1

Synthesis Example 6

5 kg (10 moles) of 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene and 40.5 kg of N, N-dimethylacetamide in a reaction vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube. Put it. After the mixture is cooled to approximately 0 ° C., 2.147 kg (9.85 mole) of pyromellitic dianhydride is added by dividing the solution in 5 parts while paying attention to the temperature rise of the solution under nitrogen atmosphere. Then, the temperature of the reaction mixture is increased to room temperature and the room temperature is increased. Stir for 20 hours.

To the resulting polyamic acid solution, 2.02 kg (20 moles) of triethylamine and 2.55 kg (25 moles) of acetic anhydride were added dropwise at room temperature under a nitrogen atmosphere and stirred at room temperature for about 20 hours to give a yellow slurry. Get The slurry was filtered to obtain a light yellow polyimide powder. The polyimide powder was sludged with methanol, filtered, and dried at 150 ° C. for 8 hours under reduced pressure to yield 6.6 kg (about 97.5%) of light yellow polyimide. Get powder. The glass transition temperature Tg of this powder was 235 ° C according to the DSC method, and the inherent viscosity was 0.86 dl / g.

Synthesis Examples 7 to 10

Various polyimides are obtained by using the same process as in Synthesis Example 6 using various combinations of diamine and tetracarboxylic dianhydride. Table 2 shows the synthesis conditions, intrinsic viscosity, and glass transition temperature of the polyimide powder.

TABLE 2

EXAMPLES 1-4

The polyimide powder obtained in Synthesis Example 1 was dry mixed with an aromatic polysulfone powder VICTREX PES 3600P (trade name: Inperial Chemical Industry) under various compositions shown in Table 1. The mixture is melted, kneaded and extruded at 330-360 ° C. in an extruder with a screw of 40 mm diameter and a 3.0 / 1 extrusion ratio to obtain uniform pellets.

The pellet thus obtained was injection molded at an injection temperature of 360 ° C. and a mold temperature of 180 ° C., and physical and thermal properties of the molded product were measured and the results are shown in Table 3.

In Table 3, the glass transition temperature Tg is measured according to the TMA penetration method.

Comparative Example 1

The same process as in Examples 1 to 4 is carried out using the composition with the scope of the present invention. The physical and thermal properties of the molded article were measured and the results are shown in Table 3.

TABLE 3

[Examples 5 to 7 and Comparative Example 2]

The polyimide powder obtained in Synthesis Example 2 was dry blended with an aromatic polysulfone, VICTREX PES 3600P and the composition shown in Table 2, and pelletized by performing the same steps of Examples 1 to 4 at 320 to 360 ° C.

The obtained pellet was injection molded at a mold temperature of 190 ° C. and an injection temperature of 380 ° C., and the physical and thermal properties of the molded article were measured and the results are shown in Table 4.

TABLE 4

[Examples 8 to 10 and Comparative Example 3]

The polyimide powder obtained in Synthesis Example 3 was dry blended with an aromatic polysulfone powder, UDEL POLY-SULFONE P-1700 (trade name: Union Carbide Corp.) and various compositions shown in Table 11. The mixture is melted, kneaded and extruded at 360 to 390 ° C. in an extruder with a screw of 40 mm diameter and a 3.0 / 1 compression ratio to obtain uniform pellets.

The pellet thus obtained was injection molded at an injection temperature of 390 ° C. and a mold temperature of 190 ° C., and the physical and thermal properties of the molded product were measured and the results are shown in Table 5.

TABLE 5

[Examples 11 to 13 and Comparative Example 4]

Polyimide powder obtained in Synthesis Example 4 and UDEL POLYSULFONE P-1700 were subjected to the same process as in Examples 1 to 4, but were treated at 370 to 390 ° C. to obtain uniformly blended pellets.

The obtained pellet was injection molded at a mold temperature of 180 ° C. and an injection temperature of 390 ° C., and the physical and thermal properties of the molded product were measured and described in Table 6.

TABLE 6

[Examples 14 to 16 and Comparative Example 5]

The polyimide powder and the aromatic polysulfone UICTREX PES 3600P obtained in Synthesis Example 5 were subjected to the same process as in Examples 1 to 4, but were treated at 370 to 390 ° C. to obtain uniformly blended pellets. The obtained pellet was injection molded at a mold temperature of 180 ° C. and an injection temperature of 390 ° C., and the physical and thermal properties of the molded article were measured and the results are shown in Table 7.

TABLE 7

[Examples 17-19]

The polyimide powder obtained in Synthesis Example 6 was dry blended with an aromatic polysulfone powder, UDEL POLYSULFONE P-1700 and various compositions shown in Table 8. This mixture is injected and pelletized at 300 to 330 ° C. of a twin screw extruder.

The obtained pellets were injection molded at a cylinder temperature of 330 to 360 ° C. and a mold temperature of 150 ° C., and the physical and thermal properties of the molded product were measured and the results are shown in Table 8.

Comparative Example 6

The same processes as in Examples 17 to 19 are carried out using compositions outside the scope of the present invention. The physical and thermal properties of the molded article were measured and the results are shown in Table 8.

TABLE 8

[Examples 20-27 and Comparative Examples 7-10]

The polyimide powders obtained in Synthesis Examples 7 to 10 are mixed with an aromatic polysulfone, wherein VICTREX PES 3600P and UDEL POLYSULFONE P-1700 are used as the aromatic polysulfone. This mixture is melted and kneaded in an extruder with the composition shown in Tables 9-11 to obtain uniformly blended pellets.

The obtained pellets were injection molded under the same conditions as in Examples 17 to 19, and the physical and thermal properties of the molded articles were measured, and the results are shown in Tables 9 to 11.

TABLE 9

TABLE 10

TABLE 11

The present invention basically provides a polyimide resin composition having good processability in polyimide having excellent properties.

Claims (2)

expression (Wherein X represents a phenylene dicarbonyl group in which the position of two carbonyl groups in a direct, thio group, or benzene ring is meta or para), and R is an aliphatic group having 2 or more carbon atoms, a cyclic aliphatic group, or a monocyclic type. 99.9 to 50% by weight of a polyimide having a repeating unit represented by an aromatic group, a condensed polycyclic aromatic group and a tetravalent group selected from the group consisting of non-condensed polycyclic aromatic groups which are directly or interconnected by a bridging member. Resin composition consisting of 0.1 to 50% by weight of polysulfone. The compound of claim 1, wherein R is Polyimide resin composition characterized in that four selected from the group consisting of.