JPH0681805B2 - Aromatic polysulfone resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a molding resin composition. More specifically, it relates to an aromatic polysulfone resin composition having excellent heat resistance, chemical resistance, mechanical strength and the like, and excellent moldability.

[Conventional technology]

Conventionally, aromatic polysulfone resins have excellent mechanical workability, heat resistance, mechanical strength, dimensional stability, flame resistance, and electrical insulation properties. It is used in fields such as transportation equipment, and is expected to be widely used in fields where co-heat resistance is required in the future.

However, since the polysulfone resin is placed in a polar solvent such as halogenated hydrocarbons and ketones, there is a problem that its chemical resistance is insufficient. Further, although the polysulfone resin is excellent in heat resistance and mechanical strength, it is not satisfactory as compared with a high heat resistant resin represented by a polyimide resin, a polyamideimide resin or the like.

[Problems to be solved by the invention]

An object of the present invention is to obtain a polysulfone resin composition having improved chemical resistance, mechanical strength, and heat resistance in addition to the excellent properties of aromatic polysulfone.

[Means for solving problems]

As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition comprising an aromatic polysulfone and a specific amount of novel polyetherimide is particularly effective for the above purpose. Completed the invention.

That is, the present invention, relative to 100 parts by weight of aromatic polysulfone,
Next (I) Represents an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group,
Represents a tetravalent group selected from the group consisting of a monocyclic aliphatic group, a condensed polycyclic aromatic group, and a non-condensed cyclic aromatic group in which aromatic groups are linked directly or by a bridging member). An aromatic polysulfone resin composition comprising 1 part by weight or more and less than 100 parts by weight of a polyetherimide resin having the repeating unit shown.

The aromatic polysulfone used in the present invention is A polysulfone having a repeating unit such as "VICTREX PE from the UK
Polyethersulfone marketed under the trademark S "and / or the general formula "UDEL POLY
Mention may be made of the polysulfones marketed under the trademark "SULFONE".

As these aromatic polysulfones, those having various degrees of polymerization can be freely produced, and those having a melt viscosity characteristic suitable for a target blend can be arbitrarily selected.

The polyetherimide resin used together in the present invention for the purpose of improving the chemical resistance, heat resistance and / or mechanical strength of the aromatic polysulfone is represented by the following formula (I) A polyetherimide resin comprising repeating units of the formula (wherein X is the same as above), and the present inventor has excellent mechanical properties, thermal properties, electrical properties, solvent resistance and the like, and has excellent heat resistance. Found as a polyimide possessed (Japanese Patent Application No. 60-18841
4) which has the formula (IV) as the diamine component. Represented by ether diami, that is, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene and / or 1,
3-bis [4- (3-aminophenoxy) benzoyl] benzene is used, and a polyamic acid obtained by reacting these with one or more tetracarboxylic acid dianhydrides is obtained by dehydration cyclization. It is an ether imide.
Further, known diamines used for producing other polyimides may be used in combination within the range not impairing the properties of polyetherimide. Examples of diamines that can be used in combination include, for example, metaphenylenediamine,
Para-phenylenediamine, ortho-phenylenediamine,
m-aminobenzylamine, p-aminobenzylamine, 3,3'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfoxide, 3,3'-diaminodiphenyl sulfone, 3,3 ′ -Diaminobenzophenone, 3,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfoxide, 3,
4'-diaminodiphenyl sulfone, 3,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether,
4,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminobenisophenone, bis [4- (3-aminophenoxy) phenyl] Methane, bis [4- (4-aminophenoxy) phenyl] methane,
1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-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-butane [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, 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 (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] sulfide, bis [4- (4
-Aminophenoxy) phenyl] sulfide, bis [4
-(3-aminophenoxy) phenyl] sulfoxide,
Bis [4- (4-aminophenoxy) phenyl] sulfoxide, Bis [4- (3-aminophenoxy) phenyl] sulfone, Bis [4- (4-aminophenoxy) phenyl] sulfone, Bis [4- (3-amino) Phenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 4,4-'[4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4-'bis [4- (4-amino-α, α-
Examples thereof include dimethylbenzyl) phenoxy] diphenyl sulfone, and these known diamines are usually used in an amount of 30% or less, preferably 5% or less. The polyetherimide used in the present invention is obtained by reacting the diamine and tetracarboxylic dianhydride in an organic solvent and dehydrating and ring-closing.

The tetracarboxylic dianhydride used at this time has the formula (Wherein R is the same as above).

That is, as the tetocalarbonic acid dianhydride used,
Ethylene tetracarboxylic acid dianhydride, butane tetracarboxylic acid, cyclopentane carboxylic acid dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetocarboxylic acid dianhydride, 2,2' , 3,3'-benzophenone tetracarboxylic acid dianhydride, 3,3 ', 4,4'-biphenyltetocarboxylic acid dianhydride, 2,2', 3,3'-biphenyltetocarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride Anhydride, 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 dianhydride, 2,3,
6,7-Naphthalenetetracarboxylic dianhydride, 1,4,5,8-
Naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetra Carboxylic acid dianhydride, 2,3,6,7-anthracene tetracarboxylic acid dianhydride, 1,2,7,8-phenanthrenetetracarboxylic acid dianhydride, etc., these tetracarboxylic acid dianhydrides alone Alternatively, two or more kinds are mixed and used.

The polysulfone resin composition of the present invention is the above polysulfone.
It is used in the range of 1 part by weight or more and less than 100 parts by weight with respect to 100 parts by weight.

In order to improve the physical properties of the polysulfone resin, particularly heat resistance, polyether imide is effective at 1 part by weight, preferably 5 parts by weight or more per 100 parts by weight of the polysulfone resin.
However, if it is used in an amount of 100 parts by weight or more, the good moldability of the polysulfone resin is lost, so it is preferable to use it in an amount less than 100 parts by weight.

Further, the polyether imide used in the present invention has substantially the same heat resistance and physical properties as compared with the conventional polyimide resin, but since it has excellent flow properties, the above-mentioned effects can be obtained by using it in combination with the polysulfone resin. It can be obtained.

When the composition according to the present invention is mixed and prepared, it can be produced by a generally known method. For example, the following method is a preferable method.

(1) Aromatic polysulfone resin powder and polyetherimide powder are pre-kneaded into a powder form by using a mortar, a Henschel mixer, a drum blender, a tumbler blender, a ball mill ribbon blender and the like.

(2) Polyetherimide powder is previously dissolved or suspended in an organic solvent, and an aromatic polysulfone resin is added to this solution or suspension to uniformly disperse or dissolve, and then the solvent is removed to form a powder. To do.

(3) After dissolving or suspending an aromatic polysulfone resin in an organic solvent solution of a polyamic acid that is a precursor of the polyetherimide of the present invention, heat treatment at 100 to 400 ° C, or
Alternatively, after chemically imidizing using a commonly used imidizing agent, the solvent is removed to obtain a powder.

The powdery resin composition thus obtained is directly used for various molding applications, that is, injection molding, compression molding, transfer molding, extrusion molding, etc., but it is more preferable to use it after melt blending. is there. Especially when mixing and preparing the composition, powders, pellets, or powders and pellets may be melted.
This is a simple and effective method.

For the melt-blending, the equipment usually used for melt-blending rubber or plastics, for example, hot roll, Banbury mixer, prabender, extruder and the like can be used. The melting temperature is set above the melting temperature of the blending system and below the temperature at which the blending system begins to thermally decompose, but the temperature is usually 280 to 420 ° C., preferably 30.
It is 0 to 400 ° C.

As a molding method of the resin composition of the present invention, extrusion molding or extrusion molding, which is a molding method of forming a homogeneous melt blend and having high productivity, is preferable, but other transfer molding, compression molding, or sintering molding is performed. There is no problem even if shape or extrusion film molding is applied.

One or more solid lubricants such as molybdenum disulfide, graphite, boron nitride, lead monoxide, and lead powder can be added to the resin composition of the present invention. It is also possible to add one or more reinforcing agents such as glass fiber, carbon fiber, aromatic polyamide, silicon carbide fiber, potassium titanate fiber and glass beads.

With respect to the resin composition of the present invention, within a range that does not impair the object of the present invention, an antioxidant, a heat stabilizer, an ultraviolet absorber, a flame retardant, a flame retardant aid, an antistatic agent, a lubricant, One or more conventional additives such as colorants can be added.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples.

Synthesis Example 1 5 kg (10 mol) of 1,3'-bis [4- (3-aminophenoxy) benzoyl] benzene and N, N-dimethylacetamide were placed in a reaction vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube. After charging 40.5 kg, the mixture was cooled to around 0 ° C., 2.147 kg (9.85 mol) of pyromellitic dianhydride was added under nitrogen atmosphere while paying attention to the rise in solution temperature, and the mixture was stirred at room temperature for about 20 hours.

2.02 kg of this polyamic acid solution in a nitrogen atmosphere at room temperature
(20 mol) triethylamine and 2.55 kg (25 mol)
Acetic anhydride was added dropwise and stirred at room temperature for 20 hours to obtain a pale yellow slurry. The slurry was filtered, washed with methanol, then filtered, dried under reduced pressure at 150 ° C for 8 hours, and 6.6 kg.
A pale yellow polyetherimide powder (yield about 97.5%) was obtained.

The logarithmic year of this polyetherimide powder was 0.86 dl / g. Here, the logarithmic viscosity is a value measured by heating and dissolving 0.5 g of polyetherimide powder in a p-chlorophenol / phenol mixed solvent (90:10 weight ratio) and then cooling to 35 ° C. (The values shown below were also measured by the same method).

The glass transition temperature of this polyetherimide powder is 23
The temperature was 5 ° C. (measured by the DSC method, and the values shown below were also measured by the same method).

Examples 1 to 4 and Comparative Examples 1 to 2 Various types of polyetherimide powder obtained in Synthesis Example 1 and aromatic polysulfone resin powder (Udel Polysulfone P-1700 manufactured by Union Carbide Co.) are shown in Table 1. After dry blending in the composition ratio of, the mixture was extruded at 300 to 330 ° C. using a twin-screw melt extruder and granulated.

Then, the pellets are injected into an injection molding machine (cylinder-temperature 330
Approximately 360 ℃, mold temperature 150 ℃) to obtain a test piece, to measure the thermal, mechanical properties and chemical resistance. Table of results
Shown in 1.

In Table-1, tensile strength and elongation at break are ASTM D-638, flexural strength and flexural modulus are ASTM D-790, and Izod impact values are
ASTM D-256, glass transition temperature is T MA penetration method, heat distortion temperature was ASTM D-648, and moldability was based on minimum injection pressure.

For chemical resistance, immerse the test piece in each chemical for 30 minutes and observe the change in appearance, ○ if there is no change, ○ if there is some change, △, if there is a large change, × when not usable It was written with.

Synthetic Examples 2 to 5 Various etherimide powders were obtained in the same manner as in Synthetic Example 1 by combining various diamines and various tetracarboxylic dianhydrides.

Synthesis Example 2 3,3-bis [4- (3-aminophenoxy) benzoylbenzene 95 mol% and 4,4'-diaminodiphenyl ether 5 mol% in a total amount of 10 mol, 3,3 ', 4,4'- Using 9.85 mol of benzophenone tetracarboxylic dianhydride, an ether imide powder having an inherent viscosity of 0.82 dl / g was obtained.

Synthesis Example 3 Using 9,85 mol of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride to 10 mol of 1,4-bis [4- (3-aminophenoxy) benzoylbenzene, a logarithmic viscosity of 0.84 dl / g The ether imide powder of

Synthetic Example 4 Pyromellitic dianhydride was added to a total amount of 10 mol consisting of 90 mol% of 1,4-bis [4- (3-aminophenoxy) benzoylbenzene and 10 mol% of 4,4'-bis (3-aminophenoxy) biphenyl. Using 9.8 mol of the product, an etherimide powder having an inherent viscosity of 0.80 dl / g was obtained.

Synthesis Example 5 1,4-bis [4- (3-aminophenoxy) benzoylbenzene 85 mol% and 4,4'-diaminophenyl ether 15 mol% in a total amount of 10 mol, bis (3,4-dicarboxyphenyl) Logarithmic viscosity of 0.78 dl / using 9.8 mol of ether dianhydride
g of etherimide powder was obtained.

Examples 5 to 16 and Comparative Examples 3 to 7 The polyetherimide powder and the aromatic polysulfone resin powder obtained in Synthesis Examples 2 to 5 were melt-kneaded at various composition ratios to obtain uniformly mixed pellets. Then, injection molding was carried out in the same manner as in Example 1, and its thermal properties , Mechanical properties and chemical resistance were measured. The results are shown in Table-2.
~ Shown in Table-5.

As shown in the results of Table-1 to Table-5, the good moldability of the aromatic polysulfone resin is maintained by using the polyetherimide in the range of 1 to 100 parts by weight based on 100 parts by weight of the aromatic polysulfone resin. However, it can be understood that various properties such as chemical resistance and heat resistance are improved.

〔The invention's effect〕

The aromatic polysulfone resin composition in the present invention has significantly improved chemical resistance, heat resistance, mechanical strength and the like in addition to the properties inherently possessed by aromatic polysulfones, and is used for aerospace equipment, electronic / electrical equipment and automobiles. It is useful in a wide range of fields such as precision equipment and general equipment, and its industrial effect is great.

Claims (3)

[Claims] 1. The following formula (I) is added to 100 parts by weight of an aromatic polysulfone resin. Represents an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group,
Represents a tetravalent group selected from the group consisting of a monocyclic aliphatic group, a condensed polycyclic aromatic group, and a non-condensed cyclic aromatic group in which aromatic groups are linked directly or by a bridging member). An aromatic polysulfone resin composition comprising 1 part by weight or more and less than 100 parts by weight of a polyetherimide resin having the repeating unit shown. 2. The aromatic polysulfone resin has the formula (II) The resin composition according to claim 1, which comprises a repeating unit of 3. The aromatic polysulfone resin has the formula (III) The resin composition according to claim 1, which comprises a repeating unit of