JPH04198354A - Production of thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition, excellent in low-temperature breaking resistance after coating and good in heat resistance and dimensional stability by separately melt kneading a modified polyphenylene ether with a rubber component and two kinds of polyamides having different solution relative viscosities. CONSTITUTION:A resin composition is obtained by previously melt kneading a polyamide having a high solution relative viscosity of (B) a polyamide resin containing polyamides having >=0.2 difference in solution relative viscosity measured by using a solution at 1.0% concentration in 98% concentrated sulfuric acid at 25 deg.C in (A) a polyphenylene ether prepared by oxidatively polymerizing phenols expressed by the formula (R<1> to R<4> are H, 1-10C alkyl, halogen, etc.) and reacting the resultant polyphenylene ether with a functional group-containing compound and (C) a rubber component such as a D-E type block copolymer (D is vinylic aromatic hydrocarbon block; B is polymerized conjugated diene block) so as to provide (5-90)/(90-5)wt.% ratio of the components (A)/(B) and 1-25 pts.wt. component (C) based on 100 pts.wt. total amount of the components (A) and (B) and then melt kneading the polyamide having a low solution relative viscosity therein.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention has excellent properties such as heat resistance, dimensional stability, impact resistance, and melt flowability. Regarding the production of a thermoplastic resin composition that exhibits excellent post-coating low-temperature fracture resistance without causing brittle fracture in the test, more specifically, a specific modified polyphenylene ether, a specific solution relative viscosity true double thermoplastic resin consisting of two homogeneous polyamides, an A-B-A' type or A-B type block copolymer elastomer, a hydrogenated A-B-A' type or A-B type block copolymer elastomer, or a modified polyolefin The composition is produced by melt-kneading a polyamide with a high relative solution viscosity with a modified polyphenylene ether and a rubber component in advance, and then melt-kneading a polyamide with a low solution relative viscosity into the resulting mixture.

[Conventional technology]

In recent years, there has been much research into creating new materials by blending two or more types of polymers. Among these, polymer blend materials that combine polyamide and polyphenylene ether as main components have good affinity for both polymers, and have excellent moldability, wear resistance, and
Since it is possible to obtain a material that combines the properties of ltIm with the excellent heat resistance, dimensional stability, and water resistance of polyphenylene ether, many study examples have been reported.

Among these, several studies have been made on kneading methods for blended yarns that are particularly well-balanced.

Examples include those in which nylon 66 is melt-kneaded with BoIJ phenylene ether and a compatibilizing agent, and the resulting mixture is further melt-kneaded with other types of polyamides (for example, JP-A-62-270654); Alternatively, a part of another type of polyamide is melt-mixed with the J4 impact modifier in advance, and the resulting mixture is melt-kneaded with the remaining polyamide and polyphenylene ether (for example, JP-A-63-1999-1).
No. 215767).

[Problem that the invention seeks to solve]

By the method of dividing and melt-kneading the same or different polyamides disclosed in the above-mentioned prior art, fFIII
It has given fairly good results in terms of basic properties such as hardness, dimensional stability, moldability, and impact resistance typified by eye shift impact strength. However, when it is assumed that the material will be used for the exterior and outer panel parts of automobiles such as phenoders, door panels, and bumpers, the above-mentioned conventional materials are not necessarily satisfactory in the drop ball test and the drop test after painting, which are close to practical evaluation. . In other words, all of the above conventional materials are extremely brittle, causing brittle fracture when subjected to a falling ball or falling weight test in the low temperature range of 0°C to -30°C, with cracks occurring in a wider area than the impact area of the ball or weight. indicate a property. This property severely limits its use in large parts such as automobile exteriors and exterior panel parts, and there is currently a strong desire to improve the low-temperature fracture resistance of this coating.

Means for Solving Problem C117] Therefore, the present inventors conducted intensive studies to obtain a polyamide/polyphenylene ether/rubber blend material that can improve the low-temperature fracture resistance after coating described above, and found that as a polyamide component, Among two homogeneous polyamides with different relative solution viscosities, the polyamide with a higher solution relative viscosity is melt-kneaded with modified polyphenylene ether and a rubber component, and the polyamide with a lower solution relative viscosity is melt-kneaded into the mixed mixture. As a result, the present inventors have discovered that the low-temperature fracture resistance after coating can be dramatically improved, which is unimaginable by simply melt-kneading polyamides of the same type or different types in sections, and have arrived at the present invention. That is, the present invention provides: (A) a polyphenylene ether obtained by oxidative polymerization of one or more phenols represented by the following formula (1); and a carboxylic acid group, a carbon By reacting 0.05 to 20 parts by weight of a substituted olefin compound having a small amount (both one type of functional group) in the molecule selected from acid anhydride groups and imide groups in the presence or absence of a radical generator. Obtained modified polyphenylene ether (B)
The difference in relative viscosity of solutions measured at 25°C at 1.0% concentration in 98% concentrated sulfuric acid of the same type of polyamide is 0.2 or more,
A polyamide resin in which the proportion of polyamide with low solution relative viscosity is 50 to 99% by weight based on the total polyamide, and the proportion of polyamide with high solution relative viscosity is 1 to 50% by weight based on the total polyamide, and (C) A-B -A' type or It A -B type block copolymer elastomer (where A and A' are vinyl aromatic hydrocarbon blocks, and B is a polymerized conjugated genoblock) or A-B- A' type or A-
Hydrogen is obtained by hydrogenating the block B portion of a B-type block copolymer elastomer (here, A and A' are vinyl aromatic hydrocarbon blocks, and B is a polymerized conjugated tene block). Addition A-B-A' type or A-s
type block copolymer elastomer, or a modified polyolefin having in its molecule at least one functional group selected from carboxylic acid groups, carboxylic acid metal bases, carboxylic acid ester bases, carboxylic acid anhydride groups, and imide groups. Consisting of at least one rubber component, the ratio of (A)/(B) components is 5 to 90/
90 to 5% by weight, component (C) is 1 to 25 parts by weight per 100 parts by weight of components (A) + (B). Of the two homogeneous polyamides for the wings, the polyamide with higher relative solution viscosity was pre-modified with polyphenylene ether,
The present invention provides a method for producing a thermoplastic resin composition, which comprises melt-kneading the thermoplastic resin composition with a rubber component, and melt-kneading the resulting mixture with a polyamide having a low relative solution viscosity.

H (here, R1, R2, R3, R4 are hydrogen atoms, carbon number 1
-10 alkyl groups, haloalkyls, aryl groups, and halogen atoms, and R1 to R4 may be the same or different from each other. ) Polyphenylene 7 ether, which is a raw material for the modified polyphenylene ether of component (A) used in the present invention, is obtained by oxidative polymerization of the phenol represented by formula (1) above. Specific examples of phenols include 2.
6-nomethylphenol, 2,6-dinitylphenol, 2.6-sibutylphenol, 2. 6-dipropylphenol, 2.6-diphenylphenol,
2-methyl-6-nitylphenol, 2-methyl-
6-tolylphenol, 2-methyl-6-methylphenol, 2-methyl-6-butylphenol, 2゜6-dimethquinphenol, 2
, 3.6-) methylphenol, 2. 3.
5. Examples include 6-titramethylphenol.

Either a homopolymer made by polymerizing these phenols alone or a copolymer made by polymerizing a mixture of two or more of these phenols can be used in the present invention. In particular, homopolymers obtained by polymerizing 2,6-dimethylphenol and 2,6-
dimethylphenol and 2. 3. 6-) A copolymer obtained by copolymerizing a mixture of methylphenols is preferably used.

The modification component of the modified carbon ether used in the present invention is a substituted olefin compound having at least one functional group selected from a carbo/acid group, a carboxylic acid anhydride group, and an imide group. As for acrylic acid,
Methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, itafonic anhydride, glutaconic anhydride, intraconic anhydride, aconitic anhydride, maleinoic anhydride
N-phenylmaleinide, N-methylmaleimide, N-ethylmaleimide and the like can be mentioned. The amount of these substituted olefin compounds used is within the range of 0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts of polyphenylene ether. If the amount of the substituted olefin compound used is less than 0.05 parts by weight, the impact resistance and heat resistance of the composition obtained by kneading the modified polyphenylene ether, polyamide, and modified polyolefin will be insufficient, and the amount used will be less than 20 parts by weight. If the amount exceeds
stomach.

The reaction between the polyphenylene ether and the substituted olefin compound is carried out in the presence or absence of a radical generator.

Examples of suitable radical generators include benzoyl peroquinide, tsucumyl peroquinide, not-t-butyl peroquinide, t-butylcumyl peroquinide, cumene hydroperoquinide, 2,5-dimethyl-2,5 -Di-t-butylbaoquine, beef san, 2,5-dimethyl-
Examples include 2,5-not-t-butylpero-cow/hequin-3, azobisisobutyronitrile, etc., and the radical generator is preferably in the range of 5 to 301 M parts per 100 parts by weight of the substituted olefin compound. However, the type and amount of the radical generator used are not limited thereto. Regarding the method of reacting polyphenylene ether with a substituted olefin compound, there is a method of reacting it in a solution using an appropriate lsM, or a method of reacting it in a solution using an appropriate lsM, or a method of reacting it in a solution with a
A mixture of polyphenylene ether, a substituted olefin compound, and a radical generator is heated at a high temperature of 350"C for 10 seconds to 30 seconds.
There is a method of reacting while melting and mixing for a minute, and any method may be used.

The proportion of the modified polyphenylene ether obtained in this way is 5 to 90f! weight%, preferably 10 to 80% by weight
It is. If the amount of modified polyphenylene ether is less than 5%, the resin composition will lack heat resistance and dimensional stability.
If it exceeds 0% by weight, the moldability of the resin composition will be impaired, which is not preferable.

The polyamide component (B) used in the present invention is a polyamide whose main components are an amino acid, a lactam, or a diamine and a dicarboxylic acid.

Specific examples of the constituent components include ε-caprolactam, enantlactam, ω-laurolactam, ε-aminocaproic acid, etc.
- Amino acids such as amino undecanoic acid and 12-aminododecanoic acid, tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2. 2. 4-/2. 4
．． 4-Trimethyl to bovine methylenediamine, 5-methylnonamethylenenoneamine, m-ki/lyle-7noamine, p
-quinolylenodiamine, l,3-bisaminomethyl/clohexano, 1,4-bisaminomethyl/chlorhexane, bis-p-aminochlorohexyl/lumetano, bis-p-amine/clohexyl/rubrovano, isoshirondiamine, etc. noamino, anovic acid, suberinoic acid,
Azelaic acid, Sepatunoic acid, Dodecanniic acid, 1.4
-7 black bovine dicarboxylic acid, 1. Examples include dicarboxylic acids such as 3-chlorohexanenocarboxylic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and dimer acid. These constituent components may be used alone or in the form of a mixture of two or more in the polymerization, and both the polyamide homopolymer and copolymer thus obtained can be used in the present invention. Particularly useful polyamides in the present invention include polycaproamide (nylon 6), polyhexamethyleneadipamide (nylon 66), polyhexamethylene sebaamide (nylon 610), polyundecaneamide (nylon 11), polydodecanamide (nylon 12), and copolymers and mixtures of these polyamides.

These polyamides are homogeneous and 10% in 98% concentrated sulfuric acid.
The relative viscosity of the solution measured at 25° C. is 0.2 or more, preferably 0.3 or more. If the solution relative viscosity difference is less than 0.02, the low temperature fracture resistance after coating will be insufficient, which is not preferable.

The proportion of the polyamide according to the invention is from 5 to 90% by weight, preferably from 10 to 80% by weight. If the polyamide content is less than 5% by weight, the melt flowability and chemical resistance of the resin composition will be insufficient, and if the polyamide content exceeds 90% by weight, the water resistance and dimensional stability will be insufficient.

The ratio of the two homogeneous polyamides having a relative solution viscosity in the present invention is 50 to 99% by weight of the polyamide with a low solution relative viscosity, and 1 to 50% by weight of the polyamide with a high solution relative viscosity, based on the total polyamide. If the amount of polyamide with a low relative solution viscosity is less than 50% by weight, or if the amount of polyamide with a high relative solution viscosity exceeds 50% by weight, the low temperature fracture resistance after coating is undesirable.

Of the two homogeneous polyamides with different relative viscosities,
A polyamide having a high relative solution viscosity is melt-kneaded in advance with a modified polyphenylene ether and a rubber component, and a polyamide having a low solution relative viscosity is melt-kneaded into the resulting mixture. If two similar polyamides with different relative solution viscosities are mixed together or a polyamide with a low solution relative viscosity is melt-kneaded with modified polyphenylene ether and a rubber component in advance, and a polyamide with a high solution relative viscosity is melt-kneaded into the resulting mixture, the resistance after painting will be improved. Although the low-temperature rupture property is improved to some extent, it is insufficient and therefore not preferable.

A to B-A' used as rubber component (C) in the present invention
A type or A-B type block copolymer elastomer is an A-B-A' type or A-B type block copolymer elastomer consisting of a vinyl aromatic hydrocarbon and a conjugated diene. ' may be the same or different, and is a thermoplastic homopolymer or copolymer derived from a vinyl aromatic hydrocarbon whose aromatic moiety may be monocyclic or polycyclic. Examples of such vinyl aromatic hydrocarbons include ethylene,
Examples include α-methylstyrene, vinyltolueno, vinylky/lene, ethylvinylky/lene, vinylnaphthalene, and mixtures thereof.

Pro and RiB consist of conjugated geno-based hydrocarbons, such as 1,3-butadiene, 2,3-methylbutadiene,
Polymers derived from isoprene, 1,3-pentageno and mixtures thereof, and the like.

Further, the hydrogenated A-B-A' type or A-B type block copolymer elastomer refers to a part or all of the block B of the A-B-A' type or A-B type block copolymer elastomer. For example, it is an elastic body obtained by hydrogenation according to the method shown in US Pat. No. 3,431,323.

Modified polyolefins include ethylene, propylene, butene-1, pentene-1,4-methylpentene-
1, inbutylene, 114-h-t-sadiene, tunoclopentadiene, 215-norbornadiene,
5-ethylidene norporin, 5-ethyl-2,5-
norbornadiene, 5-(1″-propenyl)-2
- A polyolefin obtained by radical polymerization of at least one kind of olefin 7 selected from fluoridyl and ethylene, a cardic acid group, a carboxylic acid ester group,
It is a modified polyolefin obtained by introducing a jIffi component (hereinafter referred to as a functional group-containing component) having at least one functional group selected from a cardi/acid metal base, a carboxylic acid anhydride group, and an imide group. . Examples of functional group-containing components are acrylic acid and methacrylic acid.

Maleic acid, fumaric acid, itafluoric acid, crotonoic acid.

Methylmaleinoic acid, methylfumaric acid, mesaconic acid.

Ntraconic acid, glutaconic acid, and metal salts of these carboxylic acids, methyl hydrogen maleate, methyl hydrogen itaconate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxy/ethyl acrylate, methacrylic acid Methyl acid, 2-ethylhexyl itacrylate,
Hydroxy/ethyl methacrylate, aminoethyl methacrylate, dimethyl maleate.

Dimethyl itaconate, maleic anhydride, itanionic anhydride, anhydrous anhydride
Noic acid, Enodobi/Riro (2°2.1)-5-hebutene-2,3-nocarbonoic acid.

Entobi/Chlo(2,2,1)-5-hebutene-2,3
-dicarboxylic acid anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-femylmaleimide, and the like.

The method of introducing these functional group-containing components is not particularly limited (methods such as mixing with the main component olefins and copolymerizing them, or grafting them into polyolefins using a radical initiator can be used). .The amount of functional group-containing component introduced is 0.00 based on the entire modified polyolefin.
A suitable range is 1 to 40 mol%, preferably 0.01 to 35 mol%.

Specific examples of modified polyolefins particularly useful in the present invention
c is an ethylene/acrylic acid copolymer, an ethylene/methacrylic acid copolymer, and some or all of the carboxylic acid moieties in these copolymers with sodium or lithium.
um, potassium, zinc, cal
Salts with silicon, ethylene/methyl acrylate copolymers, ethylene/ethyl acrylate copolymers.

Ethylene/methyl methacrylate copolymer, Nichire 7/
Ethyl methacrylate copolymer, ethylene/ethyl acrylate-g-maleic anhydride copolymer.

(g'' represents a graft; the same applies hereinafter), ethylene/methyl methacrylate-g-maleic anhydride copolymer,
Ethylene/ethyl acrylate-g-maleimide copolymer, ethylene/ethyl acrylate-1-N-phenylmaleimide copolymer and partially saponified products of these copolymers, ethylene/propylene-g-maleic anhydride copolymer combination, ethylene/propylene/1,4-hexadiene-g-maleic anhydride copolymer, ethylene/propylene/2゜5-norbornadiene-g-maleic anhydride copolymer, ethylene/propylene-g-N-7enyl Maleimide copolymer, ethylene/butene-1-g-N
-7enylmaleimide copolymer, styrene/maleic anhydride copolymer, etc. can be used, and each of these can be used alone or in the form of a mixture.

Component (C) in the resin composition of the present invention can be used alone or in combination, and the ratio is (A)
The amount is in the range of 1 to 25 parts by weight, preferably 2 to 20 parts by weight, per 100 parts of component +(B). (C) When the amount of component is less than 1 part by weight, modified polyphenylene ether, polyamide.

It is not preferable because the impact resistance of the resin composition consisting of a rubber component is insufficient, and conversely, if it exceeds 25 parts by weight, the heat resistance and WA properties of the resin composition are impaired, so it is not preferable.
stomach.

In the present invention, the solution relative viscosity difference between two polyamides having different solution relative viscosities as component (B) must be 0°2 or more, and if it is less than 0.2, only a material with low low temperature fracture resistance after coating will be obtained. . Here, it is extremely important to melt-knead the polyamide, which has a high relative solution viscosity, with the modified polyphenysine ether and the rubber component in advance, and melt-knead the polyamide, which has a low solution relative viscosity, into the resulting mixture. Polyamides of the same type with different relative solution viscosities were melt-mixed in bulk, or a polyamide with a low solution relative viscosity was melt-kneaded in advance with modified polyphenylene ether and a rubber component, and the resulting mixture was melt-mixed with B1) amide with a high solution relative viscosity. This is because the low-temperature fracture resistance after coating is dramatically improved, and a material with an extremely low brittle fracture rate can be obtained. The detailed mechanism of action of this effect is not clear, but by melt-kneading the polyamide with a high relative solution viscosity first and melt-kneading the polyamide with a low solution relative viscosity later, the polyamide with a high relative solution viscosity, modified polyphenylene ether, and rubber mixture can be mixed. This is thought to be due to the dramatic stabilization of Morphokuji by balancing the melt viscosity of the polyamide with a low solution relative viscosity.

Modified polyphenylene ether, polyamide with high relative solution viscosity, A-B-A' type or A-B type block copolymer elastomer, or hydrogenated A-B-A'' type or A-B
There are no particular limitations on the method of kneading the block copolymer elastomer or modified polyolefin and the method of mixing the resulting mixture with polyamide having a low relative solution viscosity, and the powder of each resin.

Mixture of strips, pellets, single screw or two-wheel extruder,
220 to 350 by feeding it to a commonly known melt mixer such as Banobari mixer, Nigu, Miki 7 Nogrol, etc.
Examples include a method of kneading at a temperature of .degree.

The resin composition of the present invention may contain other additives such as pigments, dyes, reinforcing agents, fillers, and heat-resistant agents during resin mixing and molding, as long as the properties thereof are not impaired.

Antioxidants, weathering agents, flame retardants, fluidity improvers, antistatic agents, etc. can be added.

Injection molding and blow molding of the resin composition of the present invention.

Molded products formed by extrusion molding and other methods have excellent heat resistance, water resistance, 1-dimensional stability, and impact resistance, as well as low-temperature fracture resistance after painting. -1 Door anno < Nell.

It is extremely useful as exterior skin parts such as quarter panels, vannoys, subois, wheel cabs, vehicular lids, and side rails, as well as other general mechanical parts.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.

The properties described in Examples and Comparative Examples were evaluated by the following method.

(1) Melt inodenox: JISK7210 (2)
Tensile properties ASTM
D638 (3) Bending properties: ASTM D79-0 (4) Isolated impact strength: ASTM D256 (5)
Heat deformation temperature: ASTM
D648 (6) Low-temperature breakage properties after painting, using a Takashima type falling weight tester, square plate of 80 x 80 x 3 mm was tested for 120
℃, weight 10 kg, probe diameter 12,
A drop weight test was conducted by dropping a ymm weight from a height of 50 cm. A total of 10 samples were tested, and the number of samples that underwent ductile fracture was indicated to evaluate low-temperature fracture resistance.

(7) Painting
：Breastfeeding
After applying No. 1100 UN-IE-B brimer paint (manufactured by NOF Corporation), a mixture of Primack N01600 Surfacer W301PD intermediate coat paint (manufactured by NOF Corporation) and Primack PD curing agent was applied and baked at 60° C. for 30 minutes. Thereafter, a melamine 6200B505 top coat (manufactured by NOF Corporation) was applied and baked at 140"C for 30 minutes.

Reference example 1 7.6 g of anhydrous cuprous chloride and 10 g of not-t-butylamino
A toluene solution 4Q in which . After the polymerization, an acetic acid aqueous solution was added to deactivate the catalyst to stop the reaction, and after concentrating the reaction solution, a large amount of methanol was added to precipitate the polymer. Polyphenylene ether was obtained by filtering and drying the precipitated polymer.

Reference Example 2 (Production of modified polyphenylene ether) 100 parts by weight of the polyphenylene ether obtained in Reference Example 1, 1 part by weight of maleinoic anhydride and 2°5-methyl-2,5
-Not t-butylperoquin to beef sun 0. 1 part by weight of the mixture was supplied to the hopper of an extruder and melt-kneaded at a cylinder temperature of 320°C to obtain maleic anhydride-modified polyphenylene ether (A-1).

The reaction between the polyphenylene ether and maleic anhydride was confirmed by observing the IR of the modified polyphenylene ether after extracting the modified polyphenylene ether using methanol as a solvent at a bath ratio of 30.1 for 48 hours, which revealed that the IR was 1.600-1.
This was confirmed by analyzing the absorption peak of C--O in the region of 800 cm-'.

Reference Example 3 Modified polyphenylene ethers A-2 and A-3 were obtained by carrying out exactly the same operation as shown in Reference Example 2, except that the type and amount of the modified compound were changed.

Amount of modified compound added (weight parts us 100 parts by weight of polyphenylene ether) A-2N-phenylmaleimide 3
．． 0A-3 Itaconic anhydride 0.5 Implementation fill Solution relative viscosity 3. Modified polyphenylene ether (A-1) obtained in Reference Example 1 with nylon 614 loading% of 4
Double placement%, polystyrene-polybutanoene-polystyrene copolymer manufactured by Nonyl Chemical Co.
CALIFORNIA TR
-1102) After tri-blending 10% of (C-1) using a heno/el mixer, 3o■φ
Supply it to the hopper of the twin-screw kneader and keep the temperature at
The pellets were melt-kneaded and pelletized under the conditions of -280'' (Suf IJ, Woo rotation speed 20 rpm).
After vacuum drying at 0.00"C for 24 hours, the resulting pellets were tri-blended using a nylon 634% by weight mixer with a solution relative viscosity of 2.5.
Supplied to the ten-tube of the φ2-shaft kneader, cylinder temperature 2
The mixture was melted and kneaded at 80°C and a screw rotation speed of 20 rpm to form pellets. This pellet was heated at 100℃ for 2
After vacuum drying for 4 hours, injection molding was carried out under the conditions of Norinder temperature 28 BiC1 gold base 80'C to obtain test pieces for evaluating various physical properties. The properties of the test pieces are shown in Table 1, and the resin composition obtained here has excellent strength, heat resistance, and impact resistance, as well as extremely good low-temperature fracture resistance after painting, making it a practical product. It turned out to be a valuable material.

Comparative Example 1 14% by weight of nylon 6 with a solution relative viscosity of 2.5 and modified polyphenylene ether (A-1) 4 obtained in Reference Example 1
2% by weight, polystyrene-bolybutanoene-boristyreno copolymer manufactured by Nonyl Chemical Co., Ltd.
) TR-1102
(C-1) After tri-blending 10 wt.
The mixture was melt-kneaded and pelletized under the conditions of J x Woo rotation speed of 20 rpm. After vacuum drying the pellets at 100"C for 24 hours, the resulting pellets and solution had a relative viscosity of 3.0.
After tri-blending nylon 634% by weight using a henononyl mixer, the mixture was fed to the barrel of a 3011'Iφ twin-screw kneader, and the mixture was heated to the cylinder temperature. : 2 8
The mixture was melt-kneaded at 0° C. and at a rotation speed of 200 rpm to form pellets. After vacuum drying the pellets at 100° C. for 24 hours, injection molding and characteristic evaluation were performed in exactly the same manner as in Example 1, with the results shown in Table 1. The resin composition obtained here lacks low-temperature fracture resistance after coating.

Comparative Example 2 634% by weight of nylon with a solution relative viscosity of 2.5, 1% by weight of nylon 6 with a solution relative viscosity of 3.0, 42% by weight of the modified polyphenylene ether obtained in Reference Example 1, nonyl.
Chemical Co., Ltd. polystyrene-bolybutadiene-bolystyrene copolymer *TR-1102) (C-1) 1
After tri-blending the 0% overlay using a Hen7 El mixer, it was supplied to the hopper of a 301φ twin-screw kneader, and the cylinder temperature was 280°C and the screw rotation speed was 20 rpm.
The mixture was melt-kneaded and pelletized under the following conditions. After vacuum drying this bere-ato at 100° C. for 24 hours, injection molding and characteristic evaluation were carried out in exactly the same manner as in Example 1, and the results shown in Table 1 were obtained. The resin composition obtained here had insufficient low-temperature fracture resistance after painting.

Comparative Example 3 Nylon 614 weight R% with a solution relative viscosity of 2.8 and Reference Example 1
Modified polyphenylene (A-1) obtained in 42 [i% by weight, polystyrene polybutadiene-boso styrene copolymer manufactured by Nonyl Chemical Co., Ltd. ("Polystyrene])
TR-1102 (C-1
) 1011% was dry-blended using a Hen/El mixer, then fed to a popper of a 30 saφ twin-screw kneader, melt-kneaded and pelletized at a temperature of 280"C and a screw speed of 20 rpm. After vacuum drying the pellets in IQO'C for 24 hours, the resulting pellets and solution of nylon 63 with a relative viscosity of 2.7
After tri-blending 41j1% using a Hen/El mixer, it was supplied to the hot tube of a 3Qll@φ twin-screw kneader, and melted and kneaded under the conditions of a /linder temperature of 280°C and a screwdriver rotation speed of 20 rpm, and pelletized. .

After vacuum drying the pellets at 100° C. for 24 hours, injection molding and characteristic evaluation were performed in exactly the same manner as in Example 1, and the results shown in Table 1 were obtained. The resin composition obtained here had insufficient low-temperature fracture resistance after coating.

Comparative Example 4 % of nylon 634 with a solution relative viscosity of 27 and 42% of modified polyphenylene (8-1) obtained in Reference Example 1,
Polystyrene-bolybutadiene-boristyrene copolymer bicarifi made by Nonyl Chemical Co.
TR-1102 (C-1) 1
After tri-blending 0% by weight using a henonyl mixer, supplying it to a 30-φ twin screw kneader and bar,
Cylinder temperature 280℃, screw rotation speed 20O
The mixture was melt-kneaded and pelletized at rpm. After vacuum drying this pellet at 100°C for 24 hours, the obtained pellet was triblended with 614% by weight of nylon having a solution relative viscosity of 2.8 using a henonyl mixer.
The mixture was fed into a 30 mm diameter twin-screw kneader and melted and kneaded at a cylinder temperature of 280° C. and a screen rotation speed of 200 rpm to form pellets. This Pele.

After vacuum drying the sample at 100° C. for 24 hours, injection molding and characteristic evaluation were carried out in exactly the same manner as in Example 1, and the results shown in Table 1 were obtained. The resin composition obtained here had insufficient low-temperature fracture resistance after coating.

Comparative Example 5 Reference example with nylon 7627% by weight with a solution relative viscosity of 25! 40% by weight of the modified polyphenylene ether (A-1) obtained in 7. Hydrogenated polystyrene-bolybutadiene-boristyrene copolymer ("Krayton" manufactured by L Chemical Co., Ltd.)
After tri-blending 13% by weight of G1651) using a henonyl mixer, the mixture was supplied to the hopper of a 301φ twin-screw kneader, and melt-kneaded at a cylinder temperature of 280°C and a screw rotation speed of 20 rpm to form pellets. After vacuum drying this pellet at 100°C for 24 hours,
The resulting pellet and nylon 66 with a solution relative viscosity of 2.9
After tri-blending 20% by weight of different types of nylon using a henonyl mixer, it was supplied to the hopper of a 3011Ilφ twin-screw kneader, and melt-kneaded under the conditions of a linder temperature of 280°C and a screw rotation speed of 200 rpm.
).

After vacuum drying this pellet at 100° C. for 24 hours, injection molding and characteristic evaluation were performed in exactly the same manner as in the example, and the results are shown in Table 1. The resin composition obtained here lacked low-temperature fracture resistance after painting.

Examples 2 to 6 The difference in relative viscosity of solutions is 0. 2 or more polyamide, modified polyphenylene ether, A-B-A' type 2A-B type block copolymer elastomer, hydrogenated A-B-A' type,
The type and blending amount of the A-B type block copolymer elastomer and the modified polyolefin were varied, and the polyamide with a high relative solution viscosity was melt-kneaded with the modified polyphenylene ether and the rubber component in advance, and the resulting mixture was mixed with a solution having a high relative viscosity. Table 2 summarizes the properties of the molded pieces obtained by performing melt mixing, injection molding, and property evaluation in exactly the same manner as in Example 1 in which a polyamide with a low polyamide was melt-kneaded. All of the individually obtained resin compositions were found to be useful materials with excellent strength, heat resistance, impact resistance, and low-temperature fracture resistance after painting.

[Effect of the invention] The characteristics of the present invention are polyamide, polyphenylene ether,
In a blend system consisting of rubber, in particular, as a polyamide component, among two similar polyamides with different relative solution viscosities, use a polyamide with a lower relative solution viscosity than polyamide with a higher solution relative viscosity (used in combination and modified polyamide with a higher solution relative viscosity). Polyphenylene ether is melt-kneaded with the rubber component, and the resulting mixture is melt-kneaded with polyamide, which has a low relative solution viscosity.The polyamide, which has a high relative solution viscosity, is added and kneaded in advance, and the polyamide, which has a low relative solution viscosity, is added later. In this case, a significant improvement in low-temperature fracture resistance after painting can be achieved, which is unimaginable from bulk addition kneading or prior addition and kneading of a polyamide with a low relative solution viscosity, followed by post-addition and kneading of a polyamide with a high relative solution viscosity. has been achieved and has real practical value) high iphoryamide/bophenylene ether/
A rubber blend molding material is obtained.

Claims (1)

Scope of Claims: (A) A polyphenylene ether obtained by oxidative polymerization of one or more phenols represented by the following formula (1), and a carboxylic acid group and a carboxylic acid based on 100 parts by weight of the polyphenylene ether. Modification obtained by reacting 0.05 to 20 parts by weight of a substituted olefin compound having at least one functional group selected from anhydride group and imide group in the molecule in the presence or absence of a radical generator. Polyphenylene ether, (B) homogeneous polyamide and 1.0 in 98% concentrated sulfuric acid
The difference in solution relative viscosity measured at 25°C is 0.2 or more, the proportion of polyamide with low solution relative viscosity is 50 to 99% by weight based on the total polyamide, and the proportion of polyamide with high solution relative viscosity is 50 to 99% by weight based on the total polyamide. 1 to 50% by weight,
polyamide resin and (C) A-B-A' type or A-B type block copolymer elastomer (where A and A' are vinyl aromatic hydrocarbon blocks, and B is a polymerized conjugated diene block). ), or A-B-A' type or A-B type block copolymer elastomer (where A and A' are vinyl aromatic hydrocarbon blocks, and B is a polymerized conjugated diene block). Hydrogenated A-B-A' type or A-B type block copolymer elastomer in which the block B part of ) is hydrogenated, or a carboxylic acid group, a carboxylic acid metal base, or a carboxylic acid ester base , a rubber component of at least one modified polyolefin having in its molecule at least one functional group selected from carboxylic acid anhydride groups and imide groups, and the ratio of components (A) to (B) is 5. ~90/90
~5% by weight, component (C) is 1 to 25 parts by weight based on 100 parts by weight of components (A) + (B). A thermoplastic resin characterized in that, among two homogeneous polyamides, a polyamide with a high relative solution viscosity is melt-kneaded in advance with modified polyphenylene ether and a rubber component, and a polyamide with a low solution relative viscosity is melt-kneaded into the resulting mixture. Method of manufacturing the composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (Here, R^1, R^2, R^3, R^4 are hydrogen atoms,
selected from alkyl groups having 1 to 10 carbon atoms, haloarol groups, aryl groups, and halogen atoms, R^1 to R^
4 may be the same or different. )