JPH09286914A - Resin composition comprising polyamide and aromatic polysulfone - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition incorporated with a compound of a specific formula, having high heat resistance and excellent molding processability, and useful for e.g. automotive parts. SOLUTION: This resin composition is obtained by incorporating a total of 100 pts.wt. of (A) 99-1wt.% of a polyamide resin and (B) 1-99wt.% of an aromatic polysulfone resin with (C) 0.01-10 pts.wt. of a compound of the formula [X is a divalent organic group, either a (substituted) ethylene or a (substituted) trimethylene; ring structure is five-membered or six-membered cyclic; (n) is 0 or 1] (e.g. bisoxazoline, bisoxazine, specifically pref. 2,2'-bis(2-oxazoline)).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyamide and aromatic polysulfone resin composition having excellent heat resistance and good moldability. More specifically, the present invention relates to a polyamide and aromatic polysulfone resin composition which is obtained by blending a specific compatibilizing agent with polyamide and aromatic polysulfone and which has excellent heat resistance and molding processability.

[0002]

2. Description of the Related Art Polyamide resin has excellent mechanical properties and rigidity, and also has excellent moldability and processability.
Widely used in electrical and electronic parts, etc., the field of use of resin under more severe temperature conditions has increased, and resin with higher heat resistance than conventional polyamide resins such as nylon 6 resin and nylon 66 resin. Materials are desired. On the other hand, an aromatic polysulfone resin has excellent chemical stability and high heat resistance, but its molding process is difficult due to its high glass transition temperature and melt viscosity.

As a technique for improving these drawbacks of polysulfone, a resin composition comprising polysulfone and polybutylene terephthalate is proposed in Japanese Patent Publication No. 48257/1988. Japanese Patent Publication No. 2-209954 discloses a sulfone polymer composition which shows a low processing temperature by mixing a sulfone polymer and a polyester resin.

However, since the compatibility between the aromatic polyester and the aromatic polysulfone is not sufficient, the resulting blend has an unstable phase structure and has not been shown to have good properties. We have already proposed in JP-A-07-216207 a method for obtaining an aromatic polyester and an aromatic polysulfone resin composition with improved compatibilization.
On the other hand, regarding the polyamide and the aromatic polysulfone resin, heat resistance, improvement of impact resistance, JP 06-122815 A is disclosed as a technique for improving low water absorption, but is limited to a specific aromatic polysulfone, The extrusion temperature is 3
Since it is as high as 00 ° C., there is a problem that the polyamide is decomposed during molding and the polyamide component and the aromatic polysulfone component are limited. Further, JP-A-06-234914 discloses that heat resistance, moldability, mechanical properties, and chemical resistance can be improved by adding a polysulfone resin having an adjusted amount of phenolic hydroxyl groups as a third component. However, when a polysulfone resin having an adjusted amount of phenolic hydroxyl groups is used as a main component, heat resistance is improved, but when it is added as a third component, the effect of improving heat resistance is small.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to improve the compatibility between a polyamide resin and an aromatic polysulfone resin, thereby providing a polyamide and an aromatic polysulfone resin composition having high heat resistance and good moldability. To provide.

[0006]

Means for Solving the Problems As a result of intensive investigations by the present inventors, by blending a specific compound in a blend of a polyamide resin and an aromatic polysulfone resin, compatibility is improved, high heat resistance and excellent heat resistance are obtained. The present invention has been achieved by finding that the molding processability can be achieved at the same time.

That is, the present invention comprises (A) a polyamide resin of 99 to 1% by weight and (B) an aromatic polysulfone resin of 1 to 1.
With respect to 99% by weight and 100 parts by weight of the total amount of the (A) resin and the (B) resin, (C) the following general formula (I)

[0008]

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[In the formula, X is a divalent organic group selected from the group consisting of ethylene, substituted ethylene, trimethylene, and substituted trimethylene, and the ring structure is a 5-membered ring or a 6-membered ring. The substituent of the substituted ethylene or substituted trimethylene is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, and 8 to 8 carbon atoms.
20 aralkyl groups. D in the formula has 1 to 1 carbon atoms
It is a divalent organic group selected from the group consisting of an alkylene group having 0, an arylene group having 6 to 15 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, and an aralkylene group having 8 to 20 carbon atoms. Further, n in the formula is 0 or 1. ] It is a polyamide and aromatic polysulfone resin composition which mix | blends with the compound shown by these 0.01-10 weight part.

Hereinafter, the present invention will be described in detail.

Examples of the polyamide resin used in the present invention include ring-opening polymerization products of cyclic lactams, polycondensation products of aminocarboxylic acids, and polycondensation products of dibasic acids and diamines. Specifically, nylon is used. 6, aliphatic polyamides such as 6, nylon 66, nylon 610, nylon 612, nylon 11, and nylon 12, poly (meta-xylene adipamide), poly (hexamethylene terephthalamide),
Examples thereof include aliphatic-aromatic polyamides such as poly (hexamethylene isophthalamide) and poly (tetramethylene isophthalamide), and copolymers and mixtures thereof. Of these, nylon 6 and nylon 66 are preferable, and nylon 6 is particularly preferable.

The nylon 6 used in the present invention means a linear polymer obtained by polymerizing ε-caprolactam, but a monomer other than ε-caprolactam is copolymerized within a range not impairing the basic properties of nylon 6. Or it may be blended. Nylon 6
6 is a polyamide containing polyhexamethylene adipamide and hexamethylene adipamide units as main constituents. This resin is prepared by a usual melt polymerization method, that is, a substantially equimolar salt of hexamethylenediamine and adipic acid as raw materials is charged into a polymerization tank together with water and polymerized at a temperature of about 250 to 300 ° C under normal pressure, increased pressure or reduced pressure. Can be obtained by a method of performing.

The intrinsic viscosity of nylon 6 used in the present invention is preferably in the range of 1.0 to 3.0 as measured at 35 ° C. by dissolving 0.4 g of polyamide in 100 ml of m-cresol. The use of nylon 6 in excess of 3.0 is not desirable because the fluidity during molding deteriorates due to the high melting temperature. On the other hand, if the intrinsic viscosity is lower than 1.0, the mechanical strength of the molded product is lowered, which is not desirable.

The aromatic polysulfone resins used in the present invention are preferably linear thermoplastic polyarylene polyether sulfones in which the arylene units are linked by ether and sulfone groups. These are sulfone groups having a phenolic hydroxyl group and a halogen atom which are alkali metal salified in the same molecule by a reaction between an alkali metal salt of a bisphenol compound and an aromatic dihalogen compound, at least one of which contains a sulfone group. It can be obtained by the reaction of the contained aromatic compound. Aromatic polysulfones used for aromatic polysulfone resins and methods for producing the same are described in US Pat. Nos. 3,264,536, 4108837 and 4175175. Suitable aromatic polysulfone resins can be easily obtained from commercial products or can be produced by known methods. The aromatic polysulfone used in the present invention has a concentration of about 0.35 to about 0.35 measured in chloroform or another suitable solvent at 25 ° C. or another suitable temperature and a concentration of 0.2 g / 100 ml.
It has a reduced viscosity of about 1.2 dl / g, preferably about 0.38 to about 1.0 dl / g. At reduced viscosities less than about 0.35 dl / g, the composition is brittle, and reduced viscosities greater than about 1.2 dl / g have very high melt viscosities and are difficult to process from the melt. The amount of the polyamide and aromatic polysulfone resin used in the aromatic polysulfone resin composition of the present invention is 1 to 99% by weight based on the total amount of the polymer.

The compound (C) used in the present invention is represented by the following general formula (I).

[0016]

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In the formula, X is a divalent organic group, and the ring structure is
It is a 5- or 6-membered ring. Such X is ethylene,
Substituted ethylene, trimethylene and substituted trimethylene may be mentioned, and the substituent of substituted ethylene or substituted trimethylene is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, and a carbon atom. Examples include aralkyl groups having a number of 8 to 20. More specifically, as the alkyl group, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, ethylhexyl,
Nonyl, decyl and the like can be exemplified, and as the aryl group, phenyl, naphthyl, diphenyl and an aryl group represented by the following general formula (II),

[0018]

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(Here, R'is --O--, --CO--, --S--, --SO
₂ —, —CH ₂ —, —CH ₂ CH ₂ —, —C (CH ₃ ) ₂ — and so on. )
And the like, and cycloalkyl can be exemplified by cyclohexyl. Of these, X is ethylene,
Trimethylene is particularly preferred.

D in the formula is a divalent organic group, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 15 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, and 8 to 8 carbon atoms. Examples include 20 aralkylene groups. More specifically, as the alkylene group, methylene, ethylene, propylene,
Butylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, dimethylmethylene and the like can be exemplified, and as the arylene group, phenylene, naphthylene, diphenylene, and an arylene group represented by the following general formula (III),

[0021]

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(Where R'is --O--, --CO--, --S--, --SO
_Two-,-CH_Two-,-CH_TwoCH_Two― 、 ― C (CH_Three) _Two-Etc. )
And the like, and examples of cycloalkylene include cyclohexyl.
Xylene can be illustrated.

Further, n in the formula is 0 or 1.

The compound represented by the general formula (I) has a 5-membered ring as a compound called bisoxazoline and a 6-membered ring as a bisoxazine. Specifically, the following compounds can be exemplified.

2,2'-bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2,2'-bis (4,4-dimethyl-2-oxazoline), 2 , 2'-bis (4-ethyl-2-oxazoline), 2,2'-bis (4,4-diethyl-2-oxazoline), 2,2'-bis (4-propyl-2-oxazoline), 2 , 2 '
-Bis (4-butyl-2-oxazoline), 2,2'-bis (4-hexyl-2-oxazoline), 2,2'-bis (4-phenyl-2-
Oxazoline), 2,2'-bis (4-cyclohexyl-2-oxazoline), 2,2'-bis (4-benzyl-2-oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,
2'-m-phenylene bis (2-oxazoline), 2,2'-o-phenylene bis (2-oxazoline), 2,2'-p-phenylene bis (4-methyl-2-oxazoline), 2,2 '-p-Phenylenebis (4,4-dimethyl-2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2-oxazoline), 2,2'-m-phenylenebis (4,4 -Dimethyl-2-oxazoline), 2,2'-ethylenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline), 2,2'-hexamethylenebis (2-oxazoline), 2 2,2'-octamethylenebis (2-oxazoline), 2,2'-decamethylenebis (2-oxazoline),
2,2'-ethylenebis (4-methyl-2-oxazoline), 2,2 '
-Bisoxazoline compounds such as tetramethylenebis (4,4-dimethyl-2-oxazoline), 2,2'-cyclohexylenebis (2-oxazoline), 2,2'-diphenylenebis (2-oxazoline); 2 , 2'-bis (5,6-dihydro-4H
-1,3-oxazine), 2,2'-methylenebis (5,6-dihydro)
-4H-1,3-oxazine), 2,2'-ethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-propylenebis (5,6
-Dihydro-4H-1,3-oxazine), 2,2'-butylene bis (5,6-dihydro-4H-1,3-oxazine), 2,2'-hexamethylene bis (5,6-dihydro-4H -1,3-oxazine), 2,2 '
-p-phenylene bis (5,6-dihydro-4H-1,3-oxazine), 2,2'-m-phenylene bis (5,6-dihydro-4H-1,3-
Oxazine), 2,2'-naphthylene bis (5,6-dihydro-4H
-1,3-oxazine), 2,2'-p, p'-diphenylene bis (5,6
-Dihydro-4H-1,3-oxazine) and other bisoxazine compounds.

Among these compounds, 2,2'-bis (2
-Oxazoline), 2,2'-p-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline),
2,2'-bis (5,6-dihydro-4H-1,3-oxazine), 2,2'-
p-phenylene bis (5,6-dihydro-4H-1,3-oxazine), 2,2'-m-phenylene bis (5,6-dihydro-4H-1,3-
Oxazine) is preferred.

These compounds (C) can be easily prepared by a method in which a corresponding bisamide alcohol is treated with a dehydrating agent such as concentrated sulfuric acid or thionyl chloride to close the ring, or a method in which the corresponding bisamide halide is treated with an alkali to close the ring. Although it can be synthesized, it is not limited to these methods, and other methods can be appropriately used.

The amount of the compound (C) used is (A) polyamide resin 99 to 1% by weight and (B) aromatic polysulfone resin 1 to 99.
0.01 to 10 parts by weight based on 100 parts by weight of 100% by weight. If the amount is less than 0.01 part by weight, a sufficient effect of improving the compatibility cannot be seen, and if it exceeds 10 parts by weight, no further effect can be expected or the heat resistance is rather lowered, which is not preferable. A more preferable usage is 0.
05 to 5 parts by weight, particularly preferably 0.1 to 3 parts by weight.

The polyamide and aromatic polysulfone resin composition of the present invention includes other inorganic solids such as calcium carbonate, titanium oxide, feldspar minerals, clay, white carbon, carbon black, glass beads, and other granular or amorphous shapes. Fillers; plate-like fillers such as kaolin clay, talc; scaly fillers such as glass flakes, mica, graphite; fibers such as glass fibers, carbon fibers, wollastonite, potassium titanate, etc. Fillers can also be added.

In the polyamide and aromatic polysulfone resin composition of the present invention, a flame retardant, a flame retardant aid, a nucleating agent, a lubricant, an antioxidant, an ultraviolet absorber and a heat stabilizer are contained in the range which does not impair the object of the present invention. Ordinary additives such as pigments and modifiers such as impact modifiers may be included.

The polyamide and aromatic polysulfone resin composition of the present invention are prepared by using a known method such as a bumper mixer, a heating roll, a short shaft or multi-screw extruder, etc., at 230 ° C. to 360 ° C. 230 ° C-290
It can be produced by melt-kneading at a temperature of ° C.

An article obtained from the polyamide and the aromatic polysulfone resin composition of the present invention can be formed by a known method such as injection molding, extrusion molding or cast molding of the resin composition of the present invention. The composition of the present invention is a polyamide and aromatic polysulfone resin composition having excellent heat resistance and moldability, and can be used as a material for various automobile parts and electric / electronic parts.

[0033]

The present invention will be described in detail below with reference to examples. In addition, the part in an Example means a weight part. Further, the characteristics of the molded product were measured by the following methods. Mechanical properties: Tensile test Compliant with ASTM D638 Bending test Compliant with ASTM D790 Impact test Compliant with ASTM D256 Heat resistance: Compliant with deflection temperature under load ASTM D648-56

[Examples 1 and 2] Nylon 6 (Teijin Nylon NH-8001 Teijin Ltd.) was used as the component (A), and polysulfone (Teijin) was used as the component (B).
Amoco Engineering Plastics Co., Ltd. Udel P3703) was used. As the component (C), 2,2- (1,3-phenylene) -bis- (2-oxazoline) (CP resin A component manufactured by Takeda Pharmaceutical Co., Ltd.) was used, and a twin-screw extruder TEX44 (Japan Steel Works Ltd. Melt-kneading was performed at 285 ° C. and 120 rpm. The molding was carried out by using a Mitsubishi 80t injection molding machine to mold an ASTM standard piece at a cylinder temperature of 270 ° C and a mold temperature of 60 ° C, and the physical properties were measured.

[Example 3] Components (A) and (B) used were those used in Example 1. 2,2'- for component (C)
Twin screw extruder TEX using (2-bisoxazoline)
44 (manufactured by Japan Steel Works, Ltd.) was melt-kneaded at 285 ° C. and 120 rpm. For the molding, an MITSUBISHI 80t injection molding machine was used to mold an ASTM standard piece at a cylinder temperature of 270 ° C and a mold temperature of 60 ° C, and the physical properties were measured.

[Example 4] Components (A), (B) and (C) used in Example 1 were used. Impact modifiers include
Using an epoxy-modified polyolefin-acrylic acid ester copolymer (BF7M manufactured by Sumitomo Chemical Co., Ltd.), a twin-screw extruder TEX44 (manufactured by Japan Steel Works, Ltd.) at 285 ° C., 120 rp
Melt kneading was performed at m. The molding was carried out by using a Mitsubishi 80t injection molding machine to mold an ASTM standard piece at a cylinder temperature of 270 ° C and a mold temperature of 60 ° C, and the physical properties were measured.

[Comparative Example 1] As the component (A), the one used in Example 1 was used. Molding is by Mitsubishi 80t injection molding machine,
ASTM standard pieces were molded at a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C., and physical properties were measured.

Comparative Example 2 Components (A) and (B) used were those used in Example 1. Melt-kneading was performed at 285 ° C. and 120 rpm with a twin-screw extruder TEX44 (manufactured by Japan Steel Works, Ltd.). The molding was carried out by using a Mitsubishi 80t injection molding machine to mold an ASTM standard piece at a cylinder temperature of 270 ° C and a mold temperature of 60 ° C, and the physical properties were measured.

[0039]

[Table 1]

[0040]

[Table 2]

As is clear from Table 2, in each of Examples 1 to 4, heat resistance was significantly improved as compared with Comparative Examples 1 and 2, and a polyamide and aromatic polysulfone resin composition having excellent heat resistance was obtained. ing.

[0042]

According to the present invention, a polyamide and aromatic polysulfone resin composition having excellent heat resistance and good moldability can be obtained.

Claims (1)

[Claims] 1. (A) Polyamide resin 99 to 1% by weight
And (B) 1 to 99% by weight of the aromatic polysulfone resin,
Based on 100 parts by weight of the total amount of the resin (A) and the resin (B), (C) the following general formula (I): [In the formula, X is a divalent organic group selected from the group consisting of ethylene, substituted ethylene, trimethylene, and substituted trimethylene, and the ring structure is a 5-membered ring or a 6-membered ring. The substituent of the substituted ethylene or substituted trimethylene has 1 to 1 carbon atoms.
An alkyl group of 0, an aryl group of 6 to 15 carbon atoms, a cycloalkyl group of 5 to 12 carbon atoms, and an aralkyl group of 8 to 20 carbon atoms. In the formula, D is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 15 carbon atoms, and 5 to 12 carbon atoms.
And a divalent organic group selected from the group consisting of C8 to C20 aralkylene groups. Further, n in the formula is 0 or 1. ] Compound shown by 0.0
A polyamide and aromatic polysulfone resin composition, which is compounded with 1 to 10 parts by weight.