CA1262587A - Impact-resistant thermoplastic molding compounds based on polyphenylene ethers, polyoctenylenes and polyamides - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A thermosplastic resin composition, which comprises (a) from 5 to 85 parts by weight of a melted or remelted preliminary molding compound consisting of from 60 to 98 parts by weight of polyphenylene ethers, 40 to 2 parts by weight of polyoctylenes, from 0.1 to 5 parts by weight of maleic anhydride and from 0.1 to 5 parts by weight of a further acid derivative which has a melting point below 100°C and which is selected from the group consisting of an unsaturated mono- or dicarboxylic acid having up to 14 carbon atoms, an anhydride thereof, which excludes maleic anhydride, and an ester of mono- or dicarboxylic acid with an alcohol of up to 6 carbon atoms; and (b) from 95 to 15 parts by weight of an aliphatic homopolyamide or a copolyamide containing a preponderant amount of aliphatic monomer units.

Description

5~37 This is a divisional application of Serial NoO 509,477 filed May 20, 1986.
The present invention relates to a polyphenylene ether based thermoplastic molding resin.
Polyphenylene ethers (PPE) are technical high perfor-mance thermoplastic materials which have high melt viscosities and softening points. They are therefore suitable in numerous engineering applications in which stability at high temperatures is important (see US Patents 3,306,874, 3,306,875, 3,257,357 and 3,257~358). ~owever, certain properties of polyphenylene ethers make the same undesirable in many engineering applications. For example, molded parts of polyphenylene ethers are brittle, because of their poor impact resistance.
The high melt viscosities and softening points of PPEs, difficulties in processing. Further, consideration must be given to the fact that polyphenylene ethers tend to be unstable and discolor at high temperatures.
Another characteristic of polyphenylene ethers is that they are soluble in many organic solvents or swell to a large extent. This means that PPEs are unsuitable in applications where they would as a matter of course come into contact with organic solvents~
Another characteristic of polyphenylene ether resins is that their properties can be improved by mixing with other polymers. Thus, for example, blends of PPE with impact-resistant ~' ~
, :., O.Z. ~072 :: , polys-tyrenes have attained substantial technical importance ~see German Patents 2,119,301 and 2,211,005). These resln ~ompounds can be readily processed into molded parts which have sufficient impact-resistance. However, the compounded material has the dis-advan-tage that with increasing polystyrene content, the heat distortion temperature of the blends decreases when tested. These resin blends also, however, have unsatisfactory solvent resis-tance.
Compound blends of polyphenylene ethers and polyamides exhibit good flowability and also ~ood solvent resistance (see examined German Patent Application Nos. 1,694,290 and Published Unexamined Japanese Patent Application No. 78-847,390). However, such resin blends are usual.ly brittle, because the two components are incompatible and are poorly dispersable in each other.
Aromatic polyamides, such as the types which have been used and which are described, for example, in Published Unexamined European Patent Application No. 0,131,445, have poor processibility with polyphenylene ethers. However, bet-ter compatibility of both phases can be achieved by functionalizing the polyphenylene ether component, e.g., with maleic anhydride, in the presence of a radical initiator (J.5/906,452). However, the use of a radical initiator leads to an undesirable and uncontrolled partial gelling of the PPE-phase.
In view of the above stated compatability problems oE
PPE-polyamide, it has been suggested that the compatibility of both polymers can be increased by adding a sufficient quantity of . .
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a lubricant such as an organic phosphate (see Unexa~ined European Applicati.on ~o. 0,129,825) or a diamide (see Unexamined European Patent Application No. 0,115,218) to the .resin blends.
However, thi.s attempted solution to the problem is not satisfactory, because, although improved compatability is achieved, the resin blend exhibits considerably reduced heat distortion temperature.
The same disadvan-tages are characteristic of molding compounds to which copolymers of styrene and unsaturated acid derivatives have been added (see Unexamined European Patent Application 0,046,040).
Another reference, which is European Patent No.
0,024,120, discloses resinous compound blends which are composed of a polyphenylene ether, a polyamide, a third component and, appropriately, a high-molecular caoutchouc polymer. Suitable third components include liquid diene-polymers, epoxy resins or a compound having a double or triple bond and a functional group such as an acid, anhydride, ester, amino or alcohol group.
~owever,the impact resistance of the resinous compound which is obtained is insufficient for many applications. A need therefore continues to exist for a molding composition based on polypheny-lene ether which is readily processible and which exhibits improved properties.
Accordingly, it is attempted in the present invention to provide a thermoplastic resin composition which gives molded products having high solvent resistance, high impact resistance and a high heat distortion temperature under hea-t, and good phase :

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bonding which is recognizable by high elongation values at the point of tearing.
Accordingly, an aspect of the present invention provides a thermoplastic resin composition which comprises:
a) from 5 to 85 parts by weight preferably 20 to 50 parts by weight, of a melted or remelted preliminary molding compound consisting of:
60 to 98 parts by weight of a polyphenylene ether, 40 to 2 parts by weight of a polyoctylene, 0.1 to 5 parts by weight of maleic anhydride, and from 0.1 to 5 parts by weight of a further acid deriva-"~ tive which has a melting point below 100C and which is selected from the group consisting of an unsatura-ted mono- or dicaxboxylic acid having up to 14 carbon atoms, an anhydride thereof, which excludes maleic anhydride, and an ester of said mono- or dicarboxylic acid with an alcohol of up to 6 carbon atoms;
(b) from 95 to 15 parts by weiyht preferably 80 to 50 parts by weight, of an aliphatic homopolyamide or a copolyamide containing a preponderant amount of aliphatic monomer units.
Another aspect of the present invention provides a process for producing the thermoplastic resin composi-tion as defined above, comprising:
;~ (a) treating a solid mixture of the polyphenylene !
ethers and the polyoctenylenes, with maleic anhydride and said acid component;
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(b) melting the mixture obtained; and then (c) adding said polyamide to said melt.
Still another aspect of the invent:ion provides a process for production shaped articles, which process comprises molding -the thermoplastic resin composition defined above into the desired shaped article.
Ye~ further aspect of the invention provlcles a shaped article produced by molding the thermoplastic resin composition defined above.
Thermoplastic resin compositions within the scope of the present invention are those thermoplastic resin formulations which can be processed into molded articles or into semiproducts by thermoplastic processing. The thermoplastic resin compositions may be processed in gran~1lates form, Eor example. It is of importance that the molding compound is melted or remelted prior -to its use in the thermoplastic compositions.
Suitable polyphenylene ether starting materials include polyethers which are based on 2,6- dimethylphenol, with the ether oxygen of one unit being bonded to the benzene nucleus of the adjacent unit. At least 50 units should be ~oined togetherO
In principle, other o,o'-dialkylphenols can also be used, whose alkyl residue preferaby has a maximum of 6 carbon atoms, with the proviso that such molecules do not contain a tertiary carbon atom in the alkyl groups. Hcwever, phenol compounds which are substituted in the alpha position by a tertiary alkyl residue particularly a tertiary butyl resldue, only in one ortho position . ;,. . .
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can also be employed. Each of the monomer phenols mentioned may be substituted by a methyl group in the 3-position, and also in the 5-position. Mixtures of the above men-tioned monomer phenols can be used as well.
The polyphenylene ethers can be produced from the phenols, e.g~, in the presence of complex-forming agents such as copper bromide and morpholine (see German Unexamined Patent Applications 3,224,692 and 3,224,691). The viscosity numbers, determined by the procedure of DIN 53 728 in chloroform at 25C, are in the range from 35 to 80 cm3/g. A preferred polyphenylene ether is the polymer of 2,6-dimethylphenol, which is poly-(2,6-dimethyl-1,4-phenylene ether) which has a viscosity number of 40 to 70 cm3/g.
The polyphenylene ethers are usually employed :in the form of a powder or as granulates.
The polyoctenylene ingredient of the melted or remelted preliminary molding compound is produced by the ring-opening or ring-extending polymerization of cyclo-octene (see, e.g., A.
Draxler, Kautschuk, Gummi, Kunststoffe 1981, pages 185 to 190).
Polyoctenylenes having different amounts of cis- and trans double bonds, as well as different J-values and correspondingly different molecular weights, are obtainable according to methods known from the literature. Preferred polyoctenylenes are those with a viscosity number of 50 to 350 cm3/g, preferably-80 to 160 cm3/g, as determined in 0.1% solutions in toluene. These polyoctenylenes have usually from 55 to 95%, preferably 75 to 85% of the double bonds in the trans-form.

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' Various procedures may be used to produce a mixture of the polyphenylene ether and the polyoctenylene. One procedure is to dissolve both polymers in a suitable solvent, and then the mix-ture is isolated by evaporation of the solvent or by precipitation of the mixture with a nonsolvent. Another possible procedure is to unite both polymers in a melt. Further details of this procedure can be found in German Patent Application P 3 436 780.2 entitled "Thermoplastic Compounds On The Basis Of Polyphenylene Ethers And Polyoctenylenes, As Well As A Process For Their Production."
The polymer mixture which is obtained by an appropriate procedure is then treated with a mixture of maleic anhydride and the further acid derivative. This is accomplished by diefusing a liquid mixture of both acid materials into the solid melted or remelted preliminary molding compound at temperatures under 100C, preferably under 50C, under such conditions that no sticking of the granules takes place. This is achieved, for example, by large area application. ~inally the mixture is remelted at a tempera-ture of 270 to 350C.
It is very lmportant that the further acid derivative has a melting point under 100C. Suitable acid derivatives include unsaturated mono- and dicarboxylic acids having up to 14 carbon atoms, their anhydrides, except for maleic anhydride, and esters of the acids with saturated or unsaturated alcohols which have up to 6 carbon atoms. The esters of acrylic acid and of fumaric acid with saturated alcohols are preferred, especially those with n-butanol. A mixture of 0.1 to 5 parts by weight each

2~37 of maleic anhydride and the further acid derivative is used per 100 parts by weight of the total of the polyphenylene ether and the polyoc-tenylene.
Homo- and copolymers, preferably oE exclusively aliphatic s-tructure, are suitable polyamides. In particular, the 6-, 4,6-, 6,6-, 6,12-, 11- and 12-polyamides are preferred. Also suitable, however, are mixed aliphatic-aromatic copolyamides, provided the amount of fundamental aliphatic units in the polyamide is preponderant (see US Patents 2,071,250; 2,071,251, 2,130,523, 2,130,948; 2,241,322; 2,312,966; 2,512,606; 3,393,210, Kirk-Othmer, Encyclopedia of Chemical Technology, Vol.18, John Wiley & Sons (1982), pages 328 through 435). The number average molecular weight of the polyamides used Eor this purpose is usually higher than 5,000, preferably higher than 10,000.
The mixing of the polyamide ingredient with the melted or remelted preliminary molding compound treated with acid is effected by mixing the two melts into a well-kneading aggregate a-t a temperature 250 to 350C, preferably at 270 to 310C.
It is advantageous to premix the two components while dry and then to extrude them or to add the polyamide into the melt of the melted or remelted preliminary moldîng compound treated with acid.
In mixing the polyamide ingredient with the melted or remelted preliminary molding compound treated with acid, from 95 to 15 parts by weight of the molding compound treated with acid.
Preferred quantities of ingredients are 80 to 50 parts by weight ' ~

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o-f the polyamide with 20 to 50 parts by weight of the molding compound.
The thermoplastic molding resin composition may additio-nally contain unmodified or impact-resistant modified polystyrene resins. In order to obtain the desired high heat distortion temperature, the thermoplastic molding resin formulations should contain relatively small amoun-ts of the polystyrene ingredient.
The thermoplastic molding resin composition oE the invention may also additionally contain a flame retardant, as we]l as such additional ingredients as pigments, oligomers and polymers, anti-static agents, stabilizers and auxiliary processing products, as well as reinforcing agents. The amount oE the reinforcing agent shoul.d be ~lp to 50~, that of the flame retardant up to 15~ and that of all the other added substances together up to 5%. In each case the stated quantities are based on the total quantity of thermoplastic molding resin composition.
Suitable flame retardants include aromatic phosphorus compounds such as triphenylphosphine oxide and triphenylphosphate.
Conventional halogen containing flame retarding agents may also be used and these compounds include the halogen containing organic compound~ disclosed in the monograph of H. Vogel, "Flammenfestmachen von Kunststoff", Huethig-Verlag, 1966, pages 94 to 102.
However, halogenated polymers such as halogenated polyphenylene ethers (see German unexamined patent application

3,334,068) or brominated oligo- or polystyrenes can also be : .

i2~87 considered. The compounds should contain more than 30% by weight halogen D
In the event that a halogen-containing flame retarding agent is employed, it is recommended that a synergist be used.
Suitable such synergists include compounds of antimony, boron and tin. In general, they are used in quantities of 0.5 to 10 ~ by weight, based on the amount of thermoplastic molding resin compo-sitions.
Glass and carbon fibers are especially suitable as reinforcing agents.
Suitable stabilizers include organic phosphites such as didecylphenylphosphite and trilaurylphosphite, sterically blocked phenols, as well as tetramethy:Lpiperidine, benzophenone an~
triazole derivatives.
Suitable auxiliary processing agents include waxes such as oxidized carbohydrates, as well as their alkali metal salts and alkaline earth metal salts.
The thermoplastic molding resin composition obtained can be processed by the processes normally used for the processing of thermoplastics, e.g., injection molding and extrusion, into various molded articles.
Molded objects, which are used in various technical fields of application such as pipes, plates, casings and other technical products for the automotive, electrical and precision mechanics industries can be prepared from the present thermoplas-tic resin composition.

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5~37 In contrast to state-of-the-art resins, products prepared from the molding resin of the present invention are distinguished hy good high heat distortion temperature and good resistance to solvents. When the present thermoplastic resin composition is molded, it is distinguished by having a high impact resistance.
Having generally described -~his invention, a further understanding can be obtained by reference to certain specific examples which are provided herein for purposes of illustration only and are not intended to be limiting unless otherwise specified.
The viscosi~ number (J) of polyphenylene ether is measured in cm3/~ by -the procedure of DIN 53 728 at 25C in chloroform (concentration 0.5~ by weigh-t).
The notched-bar impact strength (a ) of molded objects was measured by the procedure o~ DIN 53 433 wi-th a rectangular notch at room temperature on standard small bars injection-molded at 290C.
The elongation a-t tear (epsilonR) was determined by the procedure of DI~ 53 455 on shoulder bars injection molded at The Vicat softening temperature was determined by the ; procedure of DI~ 53 699 on 4 mm thick molded articles injection-molded at 29aoc.
Exam~les Manu~acture and origin o~ the components:

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1. Polyphenylene ether Polyphenylene ether is obtained by the oxidative coupling of 2,6-dimethylphenol. The reaction is stopped when the desired J-value for the product is obtained, and the product is extracted as described in German Unexamined Patent Applications 3,313,864 and 3,332,377.
Example 1.1 A polyphenylene ether having a J-value of 55 cm3/g is produced by the procedure described above. The solvent is removed by evaporation and the melt is extruded by way of a degassing extruder. The product obtained is granulated and dried.
Example 1.2 A polyphenylene ether having a J-value of 55 cm3/g is produced in the form of a 10~ toluene solu-tion.
2. Polyoctenylenes A polyoctenylene having a J-value of 120 cm3/g and a trans-content of 80~ is used. Such a product is available commer-cially under the trademarX of VESTENAMER~ 8012 (manufacturerO
HULS AKTIENGESELLSCHAFT, D-4370 Marl 1). Additional characteris-tic data on this product can be found in the periodical"Kautschuk, Gummi, Kunststoffe",1981, pages 185 to 190, as well as in the Huls-Data Sheet No. 2247 "VESTENAMER 8012." The polyoctenylene can also be produced by the procedure described in K.J. Ivin "Olefin Metathesis," Academic Press, pages 236 ff., 1983 and in the literature references cited there.

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, ' 6~ 37 - ~3 -3. Mixture of polyphenylene ethers and polyoctenylene In the solution described in Example 1.2, -the polyoctenylene is dissolved by the procedure of Example 2, with 10 parts by weigh-t of polyoctenylene for every 90 parts by weight of polyphenylene ether. The remaining solvent is removed by means of a degassing extruder, and the product is granulated and dried.

4. Production of the melted or remelted preliminary molding compound.
To 2 kg of the mixture according to example 3 aliquid mixture (temperature 50C) of the acid derivatives, shown in Table 1 are added in small amounts in a laboratory mixer at room temper-ature, without sti.cking of the granules.
In a twin-screw kneading machine, the -thusl.y treated granules are remelted at 290C melting temperature, granulated and dried.
Table 1 Test 4.1 Test 4.2 -Quantity of the mixture of PPE and polyoctenylenes 2000 g 2000 g Quantity of maleic anhydride 20 g 20 g Further acid derivative n-butyl fumaric acrylate acid-di-n-butylester Quantity o the further acid derivative 20 g 20 q ,J

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~6~5i8'7 Comparative Test A
To 2 kg of the mixture according to example 3 is added portionally a liquid mixture of 20 g maleic anhydride and 20 g n-butyl acrylate (temperature 50C). The reaction mixture is mixed immediately with the polyamide i.e. without remelting prior to its use.
Comparative Test B
A 20 g amount of maleic anhydride is admixed in a twin-screw kneading machine to 2 kg PPE by the procedure of Example 1.1 at a melting temperature of 290C. The product is subsequently granulated and dried.
Comparative Test C
Similar to the procedure of Example B, 20 g maleic anhydride and 10 9 dicumyl peroxide are admixed with 2 kg PPE.

5. Molding compositions The mixtures produced by the procedures described in Examples 4.1,4.2, A' B and C are mixed with polyamides as describ-ed in Table 2, and the resulting mixture is remelted at 290C in a twin-screw extruder, the dispersion action of which is reinforced by kneading blocks. The material is then granulated and dried.
The product is injection molded into normal bodies and tested.
ULTRAMID~ B 4, a product of BASF AG, D-6700 Ludwigshafen, is used as a polyamide 6 compound. ULTRAMID~ A 4, a product of BASF AG, D-6700 Ludwigshafen, is used as a polyamide 66 compound. VESTAMID~ L 1900, a product of Huls AG D-4370 Marl, is used as a polyamide 12 compound.

-~ ~i2~87 Table 2 shows that the values of the elongation at tear as well as the values of the notched~bar impact strength are reduced substAntially, - if the preform is not remelted ~see comparative test A).
- if maleic anhydride is employed instead of a mixture of maleic anhydride and a further acid derivative and if PPE is used instead of a mixture of PPE and polyoctenylene.
- if an organic peroxide is employed instead of a mixture of maleic anhydride and a further acid derivative.

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' '" ',., 5l37 Having now fully described the invention, lt will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the present invention as set forth herein.

Claims (24)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY OR
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A thermoplastic resin composition, which comprises:
(a) from 5 to 85 parts by weight of a melted or remelted preliminary molding compound consisting of:
60 to 98 parts by weight of a polyphenylene ether, 40 to 2 parts by weight of a polyoctylene, 0.1 to 5 parts by weight of maleic anhydride, and 0.1 to 5 parts by weight of a further acid derivative which has a melting point below 100°C and which is selected from the group consisting of an unsaturated mono- or dicarboxylic acid having up to 14 carbon atoms, an anhydride thereof, which excludes maleic anhydride, and an ester of said mono- or dicarboxylic acid with an alcohol of up to 6 carbon atoms; and (b) from 95 to 15 parts by weight of an aliphatic homo-polyamide or a copolyamide containing a preponderant amount of aliphatic monomer units.

2. The thermoplastic resin composition of claim 1, which further comprises:
(c) at least one component selected from the group consisting of a polystyrene resin, a flame retardant and a com-pounding additive.

3. The thermoplastic resin composition of claim 1, which comprises a) from 20 to 50 parts by weight of said molding com-pound, and b) from 80 to 50 parts by weight of said polyamide component.

4. The thermoplastic resin composition of claim 1, wherein said polyamide is 6-, 4,6-, 6,6-, 6,12-, 11- or 12-polyamide.

5. The thermoplastic resin composition of claim 1, 2 or 4, wherein the number average molecular weight of said polyamides is higher than 5,000.

6. The thermoplastic resin composition of claim 1, 2 or 4, wherein the number average molecular weight of said polyamide is higher than 10,000.

7. The thermoplastic resin composition of claim 1, 2 or 4, wherein said polyphenylene ether is a polymer of 2,6-dimethyl-phenol having an intrinsic viscosity of 0.3 to 0.65 cm3/g.

8. The thermoplastic resin composition of claim 1, 2 or 4, wherein said polyoctenylene has a viscosity number of 50 to 350 cm3/g as determined in a 0.1% solution in toluene.

9. The thermoplastic resin composition of claim 1, 2 or 4, wherein said polyoctenylene has a viscosity number of 80 to 160 cm3/g as determined in a 0.1% solution in toluene.

10. The thermoplastic resin composition of claim 1, 2 or 4, wherein from 55 to 95% of the double bonds in said polyoctenylene are in the trans configuration.

11. The thermoplastic resin composition of claim 1, 2 or 4, wherein from 75 to 85% of the double bonds in said polyoctenylene are in the trans configuration.

12. The thermoplastic resin composition of claim 1, 2 or 4, wherein said ester of an unsaturated monocarboxylic acid is a C1-6 alkyl ester.

13. The thermoplastic resin composition of claim 1, 2 or 4, wherein said ester of an unsaturated monocarboxylic acid is n-butylacrylate.

14. The thermoplastic resin composition of claim 1, 2 or 4, wherein said ester of an unsaturated dicarboxylic acid is a C1-6 alkyl ester of fumaric acid.

15. The thermoplastic resin composition of claim 1, 2 or 4, wherein said ester of an unsaturated dicarboxylic acid is the di-n-butyl ester of fumaric acid.

16. A process for producing the thermoplastic resin com-position as defined in claim 1, comprising:
(a) treating a solid mixture of the polyphenylene ethers and the polyoctenylenes, with maleic anhydride and said acid component' (b) melting the mixture obtained; and then (c) adding said polyamide to said melt.

17. The process of claim 16, wherein a liquid mixture of maleic anhydride and the acid derivative is diffused into the solid mixture of polyphenylene ether and said polyoctenylene at a temperature below 100°C.

18. The process of claim 17, wherein said temperature is below 50°C.

19. A process for producing shaped articles, which process comprises molding the thermoplastic resin composition defined in claim 1 into the desired shaped article.

20. The process according to claim 19, wherein the molding is an injection molding or an extrusion molding.

21. A shaped article produced by molding the thermoplastic resin composition defined in claim 1.

22. A thermoplastic resin composition comprising: (a) from 5 to 85 parts by weight of a melted or remelted preliminary molding compound consisting of:
(i) 60 to 98 parts by weight of a polymer of 2,6-di-methylphenol having an intrinsic viscosity of 0.3 to 0.65 cm3/g, (ii) 40 to 2 parts by weight of polyoctenylene, (iii) 0.1 to 5 parts by weight (per 100 parts by weight of the total of the polyphenylene ether and the polyoctenylene) of maleic anhydride, and (iv) 0.1. to 5 parts by weight (per 100 parts by weight of the total of the polyphenylene ether and the polyoctenylene) of a further acid derivative which has a melting point below 100°C and is selected from a group consisting of a C1-6 alkyl ester of acrylic acid and a C1-6 alkyl ester of fumaric acid, and (b) from 95 to 15 parts by weight of an aliphatic polyamide.

23. The thermoplastic resin composition of claim 22, wherein said polyamide is 6-, 4,6-, 6,6-, 6,12-, 11- or 12-polyamide.

24. The thermoplastic resin composition of claim 23, wherein said further acid derivative is n-butylacrylate or di-n-butyl fumarate.