JPH0314867A - Manufacture of impact-resistant thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in both low temperature impact resistance and dimensional stability and having an appearance with good gloss by melt-compounding a polyamide resin with an intermediate composition comprising a melt-compounded material consisting mainly of a polyphenylene ether resin. CONSTITUTION:70-99wt.% polyphenylene ether resin (a) is melt-compounded with 0.1-19.9wt.% polyamide resin (b), 0.1-35wt.% impact modifier (c) (e.g. an ethylene-propylene rubber modified with maleic anhydride), and 0.01-10wt.% compound (d) having both an unsaturated group and a polar group in the same molecule (e.g. maleic anhydride) to give 100wt.% intermediate composition (A). 10-80wt.% of composition A is melt-compounded with 20-90wt.% polyamide resin (B) to give a resin composition having an improved high speed impact resistance at low temperature and rigidity well-balanced with each other and having an appearance with good gloss.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a thermoplastic resin composition that has excellent low-temperature impact resistance and dimensional stability, and has a good gloss appearance. (Prior art) Borifinilene ether resin has attracted attention as a useful resin with excellent mechanical properties and heat resistance, and is used in blends with styrene resins, etc. However, it has poor solvent resistance. In order to improve this problem, blends with polyamide (Japanese Patent Publication No. 59-41663, etc.) or blends with polyester (Japanese Patent Publication No. 51-21662, etc.) have been proposed. Furthermore, for the purpose of improving the impact strength of these blends, the combination of polyphenylene ether and polyamide,
A composition comprising a compound containing a polar group such as a carboxyl group, an imide group, an epoxy group, and a rubber substance as an impact modifier has been proposed (Japanese Unexamined Patent Publication No. 59-49753). In recent years, polyphenylene ether resin compositions that have excellent properties such as impact resistance, solvent resistance, heat resistance, moldability, and dimensional stability are being used as automobile exterior panel materials, such as fenders and door panels. However, there is now a need for even greater impact resistance. (Problems to be Solved by the Invention) Conventional polyphenylene ether resin compositions are satisfactory in high-speed impact resistance, but on the other hand, they have the drawback of large decreases in rigidity, heat resistance, and dimensional stability. In particular, in the above-mentioned applications, it is desirable that high-speed impact at low temperatures results in ductile fracture. Therefore, an object of the present invention is to improve the drawbacks of the above-mentioned resin compositions, and to provide a resin composition that has excellent low-temperature impact resistance and improved appearance gloss. (Means for Solving the Problems) As a result of intensive studies to achieve the above object, the present inventors have discovered a polyphenylene ether resin, a polyamide resin, an impact modifier, and a polyphenylene ether resin containing both an unsaturated group and a polar group. A resin composition produced by pre-blending an intermediate composition consisting of a compound and then blending a polyamide resin with it has an excellent balance of physical properties between low-temperature and high-speed impact resistance and rigidity, and has a good gloss appearance. The present invention has been achieved based on the discovery that polyphenylene ether resin (a)
70-99% by weight, polyamide resin (b) 0.1-19
．． 9% by weight, impact resistance modifier (c) 0.1-35% by weight
and a compound (d) having both an unsaturated group and a polar group in the same molecule in an amount of 0.01 to 10% by weight to obtain 100% by weight of an intermediate composition (A). ) 10 to 80% by weight of polyamide resin (B) and 20 to 90% by weight of polyamide resin (B) are melt-mixed. The polyphenylene ether resin of component (a) has structural units of the following formula: where n is at least 50
and R1, R2, R3 and R4 are each independently a hydrogen atom, a halogen atom, a hydrocarbon group containing no tertiary α-carbon atom, or a halo substituted with a halogen atom through at least two carbon atoms. Represents a -valent substituent selected from the group consisting of a hydrocarbon group, a hydrocarbon group, and a halohydrocarbon group substituted with a halogen atom through at least two carbon atoms. Examples of the above-mentioned hydrocarbon group not containing a tertiary alpha carbon atom include methyl, ethyl, proyl, isobrobyl,
Lower alkyl groups such as butyl; alkenyl groups such as vinyl, allyl, butenyl, cyclobutenyl; aryl groups such as phenyl, tolyl, xylenyl, 2,4,6-trimethylphenyl; aralkyl groups such as benzyl, phenylethyl, phenylbrobyl, etc. Listed below. Examples of the halohydrocarbon group in which halogen atoms are substituted via at least two carbon atoms include 2-chloroethyl, 2-promoethyl, 2-fluoroethyl, 2,2-dichloroethyl,
21 or 3-promobrovir, 2.2-difur sairo 3
-Iodoprovir, 2-. Examples include 3-, 4- or 5-fluoroamyl, 2-chlorovinyl, chloroethylphenyl, ethylchlorophenyl, chlorooxylyl, chloronaphthyl, promobenzyl and the like. Examples of the hydrocarbon oxy group include methoxy, ethoxy, broboxy, butoxy, phenoxy, ethylphenoxy, naphthoxy, methylnaphthoxy, benzyloxy, phenylethoxy, and tolylethoxy. Examples of the halohydrocarbonoxy group in which a halogen atom is substituted via at least two carbon atoms include 2-chloroethoxy, 2-promoethoxy, 2-chloroethoxy, 2.2
-dibromoethoxy, 2- and 3-bromobroboxy,
Examples include chloroethylphenoxy, ethylchlorophenoxy, iodoxyloxy, chloronaphthoxy, promobenzyloxy, chlorotolylethoxy, and the like. The polyphenyl ether resin used in the present invention contains 2.6
- Copolymer of dimethylphenol and 2.3.6-trimethylphenol, 2.6-dimethylphenol and 2.3
, 5.6-tetramethylphenol copolymer, 2,6
-Includes copolymers such as copolymers of diethylphenol and 2.3.6-1-limethylphenol. Further, modified polyphenylene ether such as polyphenylene ether [I] grafted with a styrene monomer (eg, styrene, p-methylstyrene, α-methylstyrene, etc.) may be used.

Methods for producing polyphenylene ether corresponding to the above are known, for example, U.S. Pat.
No. 306875, No. 3257357 and No. 32573
No. 58, as well as Japanese Patent Publication No. 52-17880 and Japanese Patent Application Laid-Open No. 50-511197.

Preferred polyphenylene ether resins for the purposes of the present invention are those with alkyl substituents in two positions ortho to the ether oxygen atom and copolymers of 2,6-dialkylphenol and 2,3,6-trialkylphenol. ．． The polyphenylene ether resin (a) used in the present invention has an intrinsic viscosity of 0.35 to 0.70 Lif!
/g (measured at 30'C in chloroform).

Next, the polyamide resin of component (b) has one -Co-NH bond in the main chain of the polymer and can be melted by heating. Typical examples thereof include nylon-4, nylon-6, nylon-6.6, nylon-4.6, nylon-12, nylon-6.10, etc. In addition, known aromatic diamines, Low crystallinity or non-quality polyamides containing monomer components such as aromatic dicarboxylic acids, transparent nylon, etc. can also be used. Preferred polyamide resins (b) are nylon-6.6,
Nylon-6 and non-grade polyamides, among which non-grade polyamides are particularly preferred. The polyamide resin (b) used in the present invention has a relative viscosity of 2.0 to 8.0 (2
(measured in 98% concentrated sulfuric acid at 5°C) is preferable. Next, examples of the impact modifier of component (c) include elastomers such as alkenyl aromatic compound-conjugated diene copolymers and polyolefin copolymers. In addition, these elastomers may contain α. Alicyclic carboxylic acids such as β-unsaturated dicarboxylic acid or endobicyclo[2.2.1]-5-hebutene-2.3-carboxylic acid or derivatives thereof are treated with peroxide, ionizing radiation, ultraviolet rays, etc. You can make use of it and use it as a graft.

If the tensile modulus of these elastomers is too high, they are insufficient as impact modifiers;
-882) or less is preferred.

Next, a compound having both an unsaturated group and a polar group in the same molecule of component (d) has an unsaturated group, that is, a carbon-carbon double bond or a carbon-carbon triple bond, and a polar group, that is, contained in the polyamide resin. It is a compound that has an amide bond at the end of the chain, a carboxyl group at the end of the chain, and a functional group that has affinity or chemical reactivity with the amine group in the same molecule. Examples of functional groups that can be darkened include the carboxyl group of carboxylic acid, groups derived from carboxylic acid, that is, various salts substituted with the hydrogen atom or hydroxyl group of the carboxyl group, esters, acid amides, acid anhydrides, imides, and acid azides. , acid halide,
Alternatively, examples thereof include xazoline, nitrile, epoxy group, amine group, hydroxyl group, and isocyanate ester.

As compounds having both an unsaturated group and a polar group, unsaturated carboxylic acids, unsaturated carboxylic acid derivatives, unsaturated epoxy compounds, unsaturated alcohols, unsaturated amines, unsaturated isocyanate esters, etc. are mainly used. Specifically, maleic anhydride, maleic acid, fumaric acid, maleimide, maleic acid hydrazide, a reaction product of maleic anhydride and diamine, for example, the following formula: (wherein R is an aliphatic group or an aromatic group unsaturated dicarboxylic acids and their derivatives such as methylnadic anhydride, dichloromaleic anhydride, maleic acid amide, itaconic acid, itaconic anhydride, soybean oil, tung oil, castor oil, Linseed oil, hempseed oil, cottonseed oil,
Natural oils and fats such as sesame oil, rapeseed oil, peanut oil, camellia oil, olive oil, coconut oil, and sardine oil; Eboxidized natural oils and fats such as eboxidized soybean oil: acrylic acid, butenoic acid, crotonic acid, vinyl acetic acid, methacrylic acid, bentene acids, angelic acid, tibric acid, 2-pentenoic acid, 3-bentenoic acid,
α-ethylacrylic acid, β-methylcrotonic acid, 4-bentenoic acid, 2-hexenoic acid, 2-methyl-2-bentenoic acid, 3-methyl-2-bentenoic acid, α-ethylcrotonic acid, 2.2- Dimethyl-3-butenoic acid, 2-hebutenoic acid, 2-octenoic acid, 4-decenoic acid, 9-undecenoic acid,
10-undecenoic acid, 4-dodecenoic acid, 5-dodecenoic acid, 4-tetradecenoic acid, 9-tetradecenoic acid, 9-hexadenoic acid, 2-octadecenoic acid, 91-year-old tadecenoic acid, icosenoic acid, docosenoic acid, erucic acid , tetracosenoic acid, mycolibenic acid, 2.4-pentadienoic acid, 2.4
-Hexadienoic acid, diallylacetic acid, geranic acid, 2.
4-decadienoic acid, 2.4-dodecadienoic acid, 9.12
-Hexadecadienoic acid, 9.12-octadecadienoic acid, hexadecatrienoic acid, linoleic acid, linolenic acid, ricinoleic acid, icosadienoic acid, icosatrienoic acid, icosatetraenoic acid, ricinoleic acid, Rheostearic acid, oleic acid, icosabentaenoic acid, erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosabentaenoic acid, tetracosenoic acid,
Hexacosenoic acid, hexacogenic acid, octacosenoic acid,
Unsaturated carboxylic acids such as traaconic acid: or esters, acid amides, and anhydrides of these unsaturated carboxylic acids:
Or allyl alcohol, crotyl alcohol, methylvinylcarbinol, allylcarbinol, methylpropenylcarbinol, 4-penten-1-ol, 1
0-undecen-1-ol, propargyl alcohol, 1,4-pentadien-3-ol, 1,4-hexadien-3-ol, 3.5-hexadien-2-ol, 2.4-hexadien-1 -ol, C nH g
l,-so H,c nH! n-? OH. c,,Hz
Alcohol represented by n-eOH (where n is a positive integer), 3-butene-1.2-diol, 2.5-dimethyl-3-hexene-2.5-diol, 1.5-hexadiene-3.4 NH. unsaturated amines substituted with groups; or low polymers such as butadiene, isobrene, etc. (e.g., with an average molecular weight of 500 to 10,0
00); or high molecular weight substances (for example, those with an average molecular weight of io.ooo or more), maleic anhydride,
Examples include allyl isocyanate, which has phenols added thereto, or has an amino group, carboxyl group, hydroxyl group, epoxy group, etc. introduced therein.

In addition, the definition of a compound that has both an unsaturated group and a polar group is as follows:
Needless to say, compounds containing two or more unsaturated groups and two or more polar groups (l!!1 or more (same type or different fl)) are included, and two or more types of compounds as component (d) are also included. It is also possible to use. Among these, more preferably,
Unsaturated dicarboxylic acids and their anhydrides such as maleic anhydride, maleic acid, itaconic anhydride, itaconic acid, unsaturated alcohols such as oleic alcohol, and eboxidized natural oils and fats, more preferably maleic anhydride, maleic acid, Among them, oleyl alcohol, eboxidized soybean oil, eboxidized linseed oil, and particularly preferred are maleic anhydride and a mixture of maleic anhydride and maleic acid. Ingredient (a) above. (b). (c) and (d) are blended in the following proportions based on 100% by weight of the intermediate composition (A). That is, the blending ratio of each component is 70 to 99% for component (a).
% by weight, preferably 74 to 97% by weight, particularly preferably 78 to 96% by weight, and component (b) is 0.1 to 19% by weight.
9% by weight, preferably 0.5 to 19% by weight, particularly preferably 1.5 to 17% by weight, and component (c) is 0.1 to 19% by weight.
35% by weight, preferably 0.5 to 25% by weight, particularly preferably 1-15% by weight, and component (d) is 0.01 to 25% by weight.
10% by weight, preferably 0.05-5% by weight, particularly preferably 0.2-2% by weight. If component (a) is less than 70% by weight, the final composition will have unsatisfactory heat-resistant stiffness and low-temperature high-speed impact strength, and if it exceeds 99% by weight, the final composition will have unsatisfactory low-temperature high-speed impact strength. Furthermore, if component (b) is less than 0.1% by weight, the low-temperature high-speed impact strength of the final composition will be unsatisfactory, while if it exceeds 19.9% by weight, the final composition will have unsatisfactory heat-resistant stiffness and low-temperature high-speed impact strength. Become. Furthermore, component (C) is O. 1% by weight
If it is less than 35% by weight, the low-temperature, high-speed impact strength of the final composition will be unsatisfactory, and if it exceeds 35% by weight, the heat-resistant rigidity of the final composition will be unsatisfactory. If component (d) is less than 0.01% by weight, the final composition will lack low-temperature, high-speed impact strength, and if it exceeds 10% by weight, the final composition will have poor appearance. The intermediate composition (A) contains the above-mentioned essential components (a). (b
). In addition to (c) and (d), various stabilizers, fluidity modifiers, impact-improving fillers (for example, granular inorganic fillers of 1P or less), heat-resistant and rigidity-improving fillers (for example, acicular or fibrous fillers with an aspect ratio of 5 or more) Optional components such as fillers) may be added to the extent that they do not significantly impair the effects of the present invention. The intermediate composition (A) is obtained by melt mixing the above components blended in a predetermined ratio. First, all the components are mixed using a Henschel mixer super mixer, a ribbon blender, a blender, etc., and then this mixture is melted using a single or twin screw extruder with L/D = 10 to 30. Knead. The melting crosstalk temperature at this time is usually in the range of 200 to 350°C. The intermediate composition (A) can be used in the production of the final composition as it is in a molten state or in the form of pellets, or it can be ground into powder and dried.

As the polyamide resin of component (B) in the second step, the polyamide listed as component (b) of the intermediate composition (A) described above can be used.

In the second step, in addition to the above-described intermediate composition (A) and polyamide (B), an impact modifier and, for example, titanium oxide,
Granular fillers such as kaolin clay, barium sulfate, and calcium carbonate; meter-shaped fillers such as Uzai Last and Tismo; fillers such as fibrous fillers such as glass fiber and carbon fiber, as well as various stabilizers, lubricants, colorants, and fluidity. Optional ingredients such as regulators, nucleating agents, antifungal agents, etc. can be added to the extent that they do not significantly impair the effects of the present invention. Intermediate composition (A) and polyamide (B) are blended in the following proportions. That is, based on the final resin composition, the intermediate composition (A) accounts for 10 to 80% by weight, preferably 15 to 75% by weight, particularly preferably 20 to 65% by weight, and (B) accounts for 20 to 9% by weight.
0% by weight, preferably 25-85% by weight, particularly preferably 35-80% by weight. If the intermediate composition (A) is less than 10% by weight, heat-resistant rigidity is insufficient, and if it exceeds 80% by weight, organic solvent resistance and low-temperature high-speed impact resistance are insufficient. Furthermore, if component (B) is less than 20% by weight, the organic solvent resistance and low-temperature high-speed impact resistance will be unsatisfactory, while if it exceeds 90% by weight, the heat-resistant rigidity will be unsatisfactory. The final resin composition of the present invention can be produced by melt-kneading, for example, using the following methods. 1) Pellet or powder intermediate composition (A)
and component (B) are mixed by the same means as for producing the intermediate composition (A) described above, and then melt-kneaded using a l-screw or twin-screw extruder with L/D = 10 to 30, Method of manufacturing the final composition. 2) Adding component (B) to intermediate composition (A) in a molten state,
A method of producing a final composition by melt-kneading using a single-screw or twin-screw extruder with L/D=lO~30. 3) Using a single-screw or twin-screw extruder with L/D = 30 to 60, the components of intermediate composition (A) are introduced from the first hopper in the state of a mixture before melt mixing, and at the same time the same extrusion is carried out. A method of producing a final composition by introducing component (B) in a solid or molten state from an intermediate hopper of a machine and melting and mixing the whole. 4) Component (B) is melt-kneaded in a single-screw or twin-screw extruder with L/D=10 to 30, and mixed with intermediate composition (A).
) in pellet form, powder form obtained by crushing pellets, or molten state, L/D = 10 to 30, uniaxial or biaxial
A method of melting and kneading these simultaneously using a shaft type extruder to produce a final composition. In the above method, the melting crosstalk temperature is usually 200 to 3
The temperature range is 50℃. The resin composition thus obtained is extruded after melt mixing,
It can be made into a pellet shape. The resin composition of the present invention can be easily molded by molding methods commonly applied to thermoplastic resins, such as injection molding, extrusion molding, and blow molding. Among these, it is preferable to use injection molding. Since the resin composition produced by the method of the present invention has good mechanical properties, it is suitable for use in parts such as interior and exterior parts of automobiles, exterior parts of electrical equipment, and office automation equipment.

(Examples) The present invention will be explained below with reference to Examples, but the scope of the present invention is not limited thereby. Example 1 (a) Polyphenylene ether resin: Intrinsic viscosity 0.51 d1/g (in chloroform at 30°C)
Poly(2,6-dimethyl-1,4-phenylene) ether was used. (b) Polyamide resin: Non-grade nylon (Novamid (c) Impact modifier: Commercially available maleic anhydride modified ethylene-brobylene rubber (
T7741P, manufactured by Nippon Gosei Rubber (maleic anhydride content: 0.5 to 1% by weight) and a commercially available hydrogenated styrene-butadiene block copolymer (Kraton Gl 65 1.
(Styrene content: 33% by weight) manufactured by Shell Co., Ltd.) was used.

(d) Compound having both an unsaturated group and a polar group in the same molecule; Commercially available maleic anhydride (reagent grade) was used. The above-mentioned components (a) and (b). (c) and (d) were thoroughly mixed in a super mixer at the blending ratio shown in Table 1. Next, this mixture was melt-kneaded using a TEX twin-screw extruder (L/D=30) manufactured by Japan Steel Works, Ltd. at a set temperature of 260°C and a screw rotation speed of 40 rpm to form a composition. It was extruded into strands and made into pellets using a cutter. This was dried in a hot air dryer at 105° C. for 8 hours. An intermediate composition was thus obtained. Seed fat shishi ■1 Yuri pear A (A) Intermediate composition; The intermediate composition produced as described above was used. (B) Polyamide resin: Nylon 6 (Ultramid B-5, manufactured by Badische Anilin und Soda Akchengesellschaft (West Germany), injection molding grade) was used. The above components were thoroughly mixed in a super mixer at the blending ratio shown in Table 1. Next, taste this using TEX manufactured by Nippon Steel Works.
Using a twin-screw extruder, the mixture was melted and mixed at a set temperature of 240°C and a screw rotation speed of 400 rpm, and then formed into pellets. The pellets of the above resin composition were injected using an in-line screw injection molding machine (Model IS-90B manufactured by Toshiba Machinery Works) at a cylinder temperature of 280°C and a mold cooling temperature of 70°C. Molding was performed and test pieces were created. In addition, just before injection molding, drying was performed for 48 hours at 0.1 mmHg and 80°C using a vacuum dryer. In addition, the injection molded test pieces were placed in a desiccator immediately after molding, and left at 23° C. for 4 to 6 days, after which an evaluation test was conducted and the results are shown in Table 2. In addition, each physical property value and various characteristics were measured by the following method. (1) Test piece (1 2
0mm x 80n++n, thickness 2n+m), load sensor dart (diameter 5/8 inch) at 11m/s
The specimen was collided at a speed of EC, the deformation and fracture behavior under the impact load was measured, and the impact energy absorbed up to the point of crack initiation in the resulting impact pattern was calculated and taken as the impact strength of the material. In addition, the fracture state of the fractured test piece was measured five times, and all five measurements showed ductile fracture of 0, 4 to 3.
Diffuse fracture is indicated by ○, 2- to 1-time ductile fracture is indicated by △, and all brittle fracture is indicated by ×. Note that the measurement ambient temperatures were -20'C and -30°C. (2) Izod impact strength ISO R180-1969 (JIS K71
10) (Izod impact strength with notch) It was measured using an Izod impact tester manufactured by Toyo Seiki Seisakusho. The measurement atmosphere temperatures were -20°C and -30°C. (3) Flexural modulus ISO R178-1974 Procedure
12 (JIS K7203) using an Instron testing machine. The measurement temperature was 23°C. (4) Surface glossiness Measured using a Nippon Denshoku Kogyo 4 gloss meter according to JIS D8741. Examples 2 to 5 The same formulation components as in Example 1 were used, except that a part of the impact modifier blended in the production of the intermediate composition in Example 1 was blended in the production of the final composition. Manufactured in a process. The composition ratio and evaluation results are shown in Table 1 and Table 2, respectively.

Comparative Examples 1 to 5 Resin compositions were manufactured using the same ingredients as in the examples, with the composition ratios shown in Table 1, and by changing the manufacturing process. That is, in Comparative Example 1, the manufacturing process of the intermediate composition was omitted, and only the polyphenylene ether resin was blended during the manufacturing of the final composition. Comparative Examples 2 to 5 were produced in two steps in the same manner as in the example except that an intermediate composition ratio different from that of the present invention was used, and in Comparative Example 1, non-quality nylon (b) and In Comparative Example 3, an intermediate composition containing no impact modifier was used, and in Comparative Example 4, non-grade nylon was used in the intermediate composition. In Comparative Example 5, a non-quality nylon whose compounding ratio in the intermediate composition exceeded the range of the present invention was used. The evaluation results are shown in Table 2.

(Effects of the Invention) The resin composition of the present invention was produced by first producing an intermediate composition mainly composed of polyphenylene ether resin based on the results of the above evaluation test, and then blending and melting polyamide resin etc. into this intermediate composition. It can be seen that the low-temperature impact strength and high-speed impact strength are significantly improved, the state of failure changes from brittle fracture to ductile fracture, and the appearance is excellent in gloss.

Therefore, according to the present invention, a resin composition can be obtained in which the high-speed impact resistance and rigidity at low temperatures are improved in a well-balanced manner, and the appearance gloss is also good, and the resin composition has a wide range of uses and can be an industrially useful material. ．．

Claims (1)

[Claims] Polyphenylene ether resin (a) 70 to 99% by weight,
Polyamide resin (b) 0.1 to 19.9% by weight, impact modifier (c) 0.1 to 35% by weight, and compound having both an unsaturated group and a polar group in the same molecule (d) 0. 01-1
0% by weight and melt-kneaded to obtain 100% by weight of intermediate composition (A).
A method for producing an impact-resistant thermoplastic resin composition, which comprises: obtaining 10 to 80% by weight of this intermediate composition (A) and then melt-kneading 20 to 90% by weight of polyamide resin (B).