JPH04216861A - Polyetherimide resin composition - Google Patents

Abstract

PURPOSE:To solve the problems in processability caused by the high melt viscosity of polyetherimide. CONSTITUTION:The title compsn. comprises 50-96 pts.wt. polyetherimide, 2-30 pts.wt. siloxane polyetherimide, and 2-30 pts.wt. arom. polyamide. The addition of the siloxane polyetherimide and the polyamide to the polyetherimide remarkably improves the flowability with little degradation in weld strength.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition containing polyetherimide.

0002

BACKGROUND OF THE INVENTION Polyetherimide has excellent flame resistance, mechanical strength and heat resistance, and is therefore used in various applications as a high-performance thermoplastic molding material. However, the polyetherimide used exhibits a high viscosity when melted, resulting in poor processability and requires high processing temperatures to reduce the viscosity. In order to avoid this problem, it is conceivable to use polyetherimide with a low degree of polymerization, but this would impair chemical resistance, mechanical strength, etc., and it would not be possible to obtain a molded article with satisfactory physical properties.

It has been proposed to incorporate small amounts of compounds such as metal soaps and fatty acid amides in order to improve processability (
JP-A-1-139645). However, this method cannot be said to be sufficient because it has little effect when used in small amounts and silver streaks are likely to occur depending on the processing temperature.

It is also known to incorporate a liquid crystal polymer (Japanese Patent Application Laid-Open No. 63-215769). but,
Although the apparent viscosity is reduced, the compatibility between the liquid crystal polymer and polyetherimide is poor, and the molded product exhibits delamination, making it unsuitable for practical use.

It is known that solvent resistance can be improved without impairing mechanical properties by incorporating crystalline polyamide (Japanese Patent Laid-Open No. 81361/1983). Further, in the example, a crystalline aliphatic polyamide is used.

It is also known that flame resistance and impact strength can be improved by incorporating siloxane polyetherimide (JP-A-1-289863). However, melt flowability is not improved.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to solve the processability problem caused by the high melt viscosity of polyetherimide.

[0008]

[Means for Solving the Problems] The object of the present invention is achieved by blending both siloxane polyetherimide and aromatic polyamide into polyetherimide, and the resin composition has good processability and moldability. The performance of the product is good.

That is, the present invention provides polyetherimide 50 to
96 parts by weight, 2 to 30 parts by weight of siloxane polyetherimide, and 2 to 30 parts by weight of aromatic polyamide.

[0010] If only siloxane polyetherimide is blended with polyetherimide, the melt fluidity will not be improved. On the other hand, when only aromatic polyamide is blended, fluidity is improved to some extent, but impact resistance and weld strength are significantly reduced. According to the present invention, when both siloxane polyetherimide and aromatic polyamide are blended into polyetherimide, the fluidity is significantly improved;
Moreover, there is little decrease in weld strength.

[0011] Polyetherimide itself is known,
It typically contains a repeating unit represented by the following formula.

0012

[Formula 1] (wherein T is -O- or a group of the formula -O-Z-O-,
The divalent bond of the group -O- or -O-Z-O- is 3,3
', 3,4', 4,3' or 4,4' position: Z is (
A)

[0013]

[Chemical formula 2],

[0014]

[Chemical formula 3],

[0015]

[C4],

[0016]

[C5],

[0017]

[C6],

[0018]

[C7] as well as

[0019]

[Chemical formula 8] and (B) general formula

[0020]

[Chemical formula 9] (wherein, X is the formula -CyH2y-,

[0021]

[Chemical formula 10],

[0022]

embedded image -O- and -S- (y is an integer from 1 to about 5)
and R is a member selected from the group consisting of divalent organic groups of (a) 6 to
aromatic hydrocarbon groups having about 20 carbon atoms and halogenated derivatives thereof; (b) alkylene groups having from 2 to about 20 carbon atoms; cycloalkylene groups having from 3 to about 20 carbon atoms; C) General formula

[0023]

[Chemical formula 12] (In the formula, Q is -S-, -O-,

[0024]

[Chemical formula 13],

[0025]

and -CxH2x-, and x is an integer from 1 to about 5).

Preferred polyetherimides further contain the following polyimide repeat units.

[0027]

[Chemical formula 15] (wherein R is as defined above and M is

[
0028

[Chemical formula 16],

[0029]

[Chemical formula 17] as well as

[0030]

[Chemical formula 18] (However, B is -S- or

[0031]

[Chemical formula 19] ).

Particularly suitable polyetherimide resins have the following general formula:

[0033]

Formula 20 (wherein, R is an aromatic hydrocarbon group having 6 to 20 carbon atoms, and n is an integer of 2 or more), ULTEM manufactured by General Electric Co. (
(registered trademark) is a typical example thereof, and its manufacturing method is disclosed in Japanese Patent Publication No. 57-9372. The polyetherimide resin must have a degree of polymerization sufficient to provide impact resistance.

Siloxane polyetherimides themselves are also known and have the formula given above for polyetherimides.

00
35]

[C21] In addition to the repeating unit of

[0036]

A repeating unit of [Image Omitted] (where T and R are as defined above, R1 is the same or different monovalent hydrocarbon group, and n and m are each an integer of 1 to about 10) and g is an integer from 1 to about 40) or the formula

[0037]

embedded image where M is as defined above and R′ is of the formula

[0038]

embedded image (wherein R1 are the same or different monovalent hydrocarbon groups, n and m are each an integer of 1 to about 10, and g is an integer of 1 to about 40) consists essentially of repeating units of

Preferably n and m are each 3,
and g has an average value in the range of about 9 to about 20.

The diamine component of the siloxane polyetherimide generally contains about 20-50 mole percent amine-terminated organosiloxane and about 50-80 mole percent other organic diamines. Preferably, the diamine component is about 25 to about 4
It contains 0 mole %, most preferably about 30 mole % amine terminated organosiloxane.

[0041] Both the polyetherimide and the siloxane polyetherimide used in the present invention can be produced by any method commonly used for producing polyetherimides. One currently preferred manufacturing method is U.S. Pat.
, 417,044.

The aromatic polyamide used in the present invention is a polyamide obtained by condensation polymerization of a salt of an aromatic dicarboxylic acid and an aliphatic diamine. As the aromatic dicarboxylic acid used to obtain the polyamide, isophthalic acid, terephthalic acid, 2-methylterephthalic acid, 2,5-dimethylterephthalic acid, etc. can be used alone or in combination of two or more. Furthermore, in addition to the above-mentioned dicarboxylic acids, aliphatic dicarboxylic acids such as succinic acid, adipic acid, suberic acid, sebacic acid, and dodecanedioic acid may be used in combination without impairing the purpose. In addition, as aliphatic diamines, tetramethylene diamine, hexamethylene diamine, 2,5
-Dimethylhexamethylene diamine, trimethylhexamethylene diamine, etc. can be used alone or in combination of two or more. When terephthalic acid and isophthalic acid are used in polyamide, the amount of terephthalic acid and isophthalic acid is 0.3 to 0.5 per mole of all monomers.
moles, and the molar ratio of terephthalic acid/isophthalic acid is
It is preferably in the range of 2/8 to 8/2. It can be obtained by using hexamethylene diamine as a diamine component. The aromatic polyamide used in the present invention is preferably amorphous. Amorphous aromatic polyamide itself is also known, and among polyamides obtained by condensation polymerization of aromatic dicarboxylic acid and aliphatic diamine, it does not exhibit crystallinity. As the aromatic dicarboxylic acid used to obtain the polyamide, isophthalic acid, terephthalic acid, 2-methylterephthalic acid, 2,5-dimethylterephthalic acid, etc. can be used alone or in combination of two or more. Further, as the aliphatic diamine, tetramethylene diamine, hexamethylene diamine, 2,5-dimethylhexamethylene diamine, trimethylhexamethylene diamine, etc. can be used alone or in combination of two or more types.

In order to obtain an amorphous polyamide, a monomer component having a structure that inhibits crystallization, ie, a side chain or ring structure, may be selected. When using isophthalic acid and terephthalic acid as the aromatic dicarboxylic acid and hexamethylene diamine as the diamine component,
If the amount of isophthalic acid is 0.3 mol or more per mol of all monomers, an amorphous polyamide can be obtained. The term "amorphous" as used herein means that the heat of crystal fusion measured by a differential scanning calorimeter (DSC) is less than 1 cal/g.

In the resin composition of the present invention, 2 to 30 parts by weight, preferably 5 to 20 parts by weight of siloxane polyetherimide, and 2 to 30 parts by weight, preferably 5 to 20 parts by weight of aromatic polyamide is blended. If the amount of siloxane polyetherimide or aromatic polyamide is less than the above, the effect of the present invention will be small. Conversely, if the amount exceeds the above range, the excellent mechanical properties and heat resistance of polyetherimide will not be exhibited in the molded article.

The composition of the present invention contains an elastomer component as an optional component for further improving impact strength, for example, based on a total of 100 parts by weight of polyetherimide, siloxane polyetherimide and amorphous aromatic polyamide. It can be included in an amount of up to 50 parts by weight.

[0046] As the elastomer component, natural rubber, butadiene polymer, styrene-isoprene copolymer, butadiene-styrene copolymer, and hydrogenated products thereof (random copolymer, block copolymer, graft copolymer, etc.) are used. ), isoprene polymer, chlorobutadiene polymer, butadiene-acrylonitrile copolymer, isobutylene polymer, isobutylene-butadiene copolymer, isobutylene-isoprene copolymer, acrylate ester polymer, ethylene-propylene copolymer Examples include polymers, ethylene-propylene-diene copolymers, thiol rubbers, polysulfide rubbers, polyurethane rubbers, polyether rubbers (eg, polypropylene oxide, etc.), epichlorohydrin rubbers, silicone elastomers, and the like.

[0047] Furthermore, the resin composition of the present invention can further contain other polymers. Examples include other polyamides such as nylon-6, nylon-6,6, and nylon-6,10 and polycarbonates, polyphenylene ethers, polyesters, polyolefins, polythioethers, polysulfides, polysulfones, polyarylates, polyetheretherketones. , fluororesin, etc.

[0048] The resin composition of the present invention may also contain, when mixing the resin, as long as it does not significantly impair its desirable properties.
During molding, other resins and additives such as pigments, dyes, reinforcing agents (glass fiber, carbon fiber, etc.), fillers (carbon flak, silica, titanium oxide, etc.), heat resistant agents, oxidative deterioration inhibitors, weathering agents, A lubricant, a mold release agent, a crystal nucleating agent, a plasticizer, a flame retardant, a fluidity improver, an antistatic agent, etc. can be added as necessary.

[0049] A preferred method for preparing the composition of the present invention is a melt-kneading method. The use of small amounts of solvent is possible, but generally not necessary. Examples of equipment include extruders, Banbury mixers, rollers, kneaders, etc., which are operated batchwise or continuously. The order of mixing the components is not particularly limited.

As polyetherimide, ULTEM1000 (General Electric Company) with different degrees of polymerization
Alternatively, ULTEM1010 (good fluidity type, General Electric Company) was used.

As siloxane polyetherimide 2,
2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 60 mol% m-phenylenediamine and 40 mol% amine-terminated dimethylpolysiloxane (where n and m are 3 and Yes, g is 9 on average
A random copolymer obtained from an amine component consisting of

As the aromatic polyamide, an amorphous aromatic polyamide consisting of a dicarboxylic acid component consisting of 70% isophthalic acid and 30% terephthalic acid and a diamine component which is hexamethylene diamine was used.

[0053] The amounts (parts by weight) of the ingredients shown in Table 1 were added to 320
A twin-screw extruder set at ℃ was used to melt and make pellets.

Test pieces for measuring various mechanical properties were molded from the pellets. The results are shown in Table 1. The measurement conditions are as follows. Melt index...ASTM
D-1238, 343.4°C, load 6.7 kg Weld strength: A tensile test piece with gates at both ends was used in accordance with ASTM D-638. Izod impact strength: ASTM D-256, notched. Tensile test...ASTM D-638H
DT...ASTM D-648, load 18.6
kg/cm2

[0055]

[Table 1] Compared to the composition of Comparative Example 1 which does not contain siloxane polyetherimide and aromatic polyamide, Example 1 has significantly improved melt flowability (melt index) and weld strength and Izod impact strength. remain equivalent. In Comparative Example 2, which does not contain siloxane polyetherimide, although the melt fluidity is improved, the weld strength is decreased and the Izod impact strength is significantly decreased. On the other hand, in Comparative Example 3, which does not contain aromatic polyamide, the impact strength is good, but the melt fluidity is significantly reduced and the weld strength is also reduced. Based on the melt index and weld strength of Comparative Examples 2 and 3, no improvement over Example 1 is expected.

In Example 2, the amount of siloxane polyetherimide was reduced, and the melt fluidity was significantly improved. However, the weld strength and impact strength are between those of Comparative Examples 2 and 3.

Examples 3 and 4 are cases in which a type of polyetherimide with good fluidity is used. Especially Example 4
The fluidity, weld strength and impact strength are all extremely excellent.

Claims (2)

[Claims] 1. A polyetherimide resin composition comprising 50 to 96 parts by weight of polyetherimide, 2 to 30 parts by weight of siloxane polyetherimide, and 2 to 30 parts by weight of aromatic polyamide. 2. The resin composition according to claim 1, wherein the aromatic polyamide is amorphous.