JP2000063664A - Polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition having well-balanced mechanical properties, low hygroscopicity, excellent dimensional stability, and desirable moldability. SOLUTION: There is provided a polyamide resin composition comprising 45-80 pts.wt. (A) polyamide resin, 3-20 pts.wt. (B) modified polyphenylene ether polymer, 5-40 pts.wt. (C) syndiotactic polystyrene polymer, and 3-35 pts.wt. (D) modified ethylene/propylene copolymer (the total of components A, B, C, and D is 100 pts.wt.), wherein component A constitutes the matrix phase, and components B, C, and D show the dispersed phase of a core/shell particulate structure composed of a shell phase constituted from components B and C having been compatibilized with each other and a core phase constituted from component D.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is excellent in various mechanical properties (especially DuPont impact value, Izod impact value, elongation, strength, elastic modulus), solvent resistance, low water absorption, dimensional stability and heat resistance. The present invention relates to a polyamide resin composition that is lightweight and is suitable for molding processability. The polyamide resin composition of the present invention can be used in a wide range of fields such as electric / electronic parts, automobile parts, machine parts and the like.

[0002]

BACKGROUND OF THE INVENTION Polyamide resins are widely used for automobile parts, electric / electronic parts and the like because they have a good balance of mechanical properties, heat resistance, chemical resistance and moldability. However, because polyamide resin absorbs water,
Due to water absorption, dimensional changes and mechanical properties such as bending strength and elastic modulus are greatly reduced, and the range of use is often greatly restricted for parts that require dimensional accuracy. Improvement is desired.

In order to improve the dimensional change of the polyamide due to water absorption, a method of blending a low water absorption polymer has been disclosed. As a specific low water-absorbing polymer,
Crystalline resins or rubbers made of polypropylene, polyethylene and their copolymers modified with unsaturated carboxylic acids and their derivatives are known. However, although the polyamide resin composition comprising this polyamide and polyolefin is recognized to have improved dimensional stability due to low water absorption, it has insufficient heat resistance and rigidity, and also has mechanical strength and heat resistance of the polyamide resin. Also, it cannot be said that it has a good balance between the moldability and the light weight and low water absorption of the polyolefin resin.

On the other hand, polyaryl ethers, especially polyphenylene ether polymers are known as engineering plastics having excellent heat resistance. Many studies have been reported for blending this polyphenylene ether polymer with a polyamide resin to produce a new material having excellent properties.

For example, in JP-A-2-305854 and JP-A-6-184436, a composition having a structure in which a polyamide is used as a matrix and a polyphenylene ether polymer containing a styrene elastomer and a modified polyolefin are dispersed However, it is difficult to maintain the balance between the fluidity and the mechanical strength at the time of molding because the retention of the elastic modulus at the time of absorbing water is inferior, and the improvement is a problem. JP-A-9-124927 discloses polyamide, polyphenylene ether polymer and ethylene-
A composition comprising an α-olefin copolymer is disclosed. With this technique, a composition excellent in impact resistance can be obtained by using an elastomer, but it is inferior in terms of rigidity, mechanical strength and heat resistance. Moreover, the improvement in moldability is insufficient.

Further, in JP-A-9-12872 and JP-A-9-31324, polyamide resin, α, β-
A resin composition comprising a polyphenylene ether polymer modified with an unsaturated carboxylic acid or a derivative thereof, an aromatic vinyl compound-aliphatic hydrocarbon copolymer, and a polypropylene resin is disclosed. This technology is useful, it has excellent mechanical strength, solvent resistance, heat resistance rigidity, low water absorption and dimensional stability, small decrease in elastic modulus when absorbing water, low specific gravity (light weight) and resin suitable for molding process. 1 illustrates a composition. However, even with this technique, there are cases in which the mechanical strength, impact resistance, heat resistance, and moldability are insufficient at the same time, and further improvement is required.

On the other hand, conventionally, a styrene polymer having a syndiotactic structure (hereinafter referred to as "SPS") has excellent heat resistance, rigidity, chemical resistance, water resistance, acid / alkali resistance, but impact resistance. Because of its poor property, its application range as a material was limited. On the other hand, a polymer having a polar group such as polyamide is excellent in moldability and heat resistance, but has high water absorption as described above, physical property change at the time of water absorption, and significant deterioration of physical properties due to acid / alkali, Improvement was desired. In order to solve such a problem, JP-A-62-257950 proposes alloying SPS with polyamide. However, SP
Compositions composed of resins that are essentially incompatible with each other such as S and polyamide cannot avoid deterioration of mechanical properties due to poor dispersibility and insufficient interfacial strength between phases.
There is a limit to the modification effect by simple blending.

Various methods using a compatibilizing agent or a rubber-like elastic body also serving as a compatibilizing agent for improving dispersibility and interfacial strength have been disclosed. For example, JP-A 1-279
In 944, a styrene-polyamide block copolymer is used, in JP-A-2-209938, a styrene-glycidyl methacrylate copolymer and a styrene-maleic anhydride copolymer are used, and in JP-A-2-219843, anhydrous. A maleic acid-modified styrene block copolymer rubber is used, and in JP-A-3-126744, a maleic anhydride-modified polyphenylene ether is used.
In Japanese Patent Laid-Open No. 116455, it is proposed to use maleic anhydride-modified SPS. In addition, JP-A-7-4848
Japanese Patent Laid-Open No. 8 proposes a method of using a compatibilizing agent and a rubber-like elastic material together. However, in any case, the mechanical properties, particularly impact resistance and elongation were insufficient, and it was not sufficient in terms of the balance among the mechanical properties, heat resistance and moldability.

[0009]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and has excellent rigidity and heat resistance suitable for use as materials for various industrial materials. The purpose of the present invention is to provide a polyamide resin composition having impact resistance and water resistance.

[0010]

[Means for Solving the Problems] The inventors of the present invention have conducted extensive studies to develop a polyamide resin composition having excellent rigidity, heat resistance, impact resistance, water resistance, etc., which satisfies the above objects. As a result, by mixing the polyamide resin with the modified polyphenylene ether polymer, the syndiotactic polystyrene resin (SPS) and the aromatic vinyl-aliphatic hydrocarbon copolymer having a specific chemical structure in a specific ratio, the polyamide resin While using as a matrix phase, the modified polyphenylene ether polymer, the SPS resin and the aromatic vinyl compound-aliphatic hydrocarbon copolymer,
The inventors have found that a polyamide-based resin composition having a core-shell type particle structure in which a secondary dispersed phase is included in a primary dispersed phase and having such excellent properties as described above can be obtained, and thus reached the present invention.

That is, in the present invention, the means for solving the above-mentioned problems is to use a polyamide resin as a matrix phase and to form a primary dispersed phase (shell phase) in a form in which a modified polyphenylene ether polymer and an SPS resin are compatible with each other. A resin composition having a structure structure in which an aromatic vinyl compound-aliphatic hydrocarbon copolymer forms a secondary dispersed phase (core phase) therein, that is, a composite particle dispersed structure having a core-shell structure Especially. Then, as specific means for realizing it, (A) polyamide resin 45 to 80 parts by weight, (B) modified polyphenylene ether polymer 3 to 20 parts by weight, (C) syndiotactic polystyrene-based polymer 5 to 40 Parts by weight, (D) aromatic vinyl compound-aliphatic hydrocarbon copolymer 3 to 35 parts by weight (however, (A) + (B) + (C) + (D) = 100 parts by weight) A) forms the matrix,
(B) and (C) are compatible with each other to form a shell phase,
(D) succeeded in obtaining a polyamide resin composition exhibiting a dispersed phase having a core-shell type particle structure forming a core phase.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The (A) polyamide resin used in the present invention is obtained by polycondensation of diamine and dicarboxylic acid, self-condensation polymerization of ω-aminocarboxylic acid, ring-opening polymerization of lactams, etc., and has a sufficient molecular weight. . Specific examples of the diamine include tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 1,
3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, bis-p-aminocyclohexylmethane, bis-p-aminocyclohexylpropane, isophoronediamine, m-xylylenediamine, p
And aliphatic, alicyclic and aromatic diamines such as xylylenediamine.

Specific examples of the dicarboxylic acid include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,
Examples thereof include aliphatic, alicyclic and aromatic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and dimer acid.
Specific examples of the ω-aminocarboxylic acid include ε-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. Examples of the lactams include ε-caprolactam, enanthlactam, ω-laurolactam and the like. In the present invention, these diamines and dicarboxylic acids, or ω-aminocarboxylic acids, or lactams are subjected to polycondensation or the like in the form of a single or a mixture of two or more kinds, and the obtained polyamide homopolymer, copolymer, And any of their homopolymers and / or mixtures of copolymers. In particular, as the polyamide resin useful in the present invention, for example, nylon 6, nylon 46, nylon 66, nylon 11, nylon 12, nylon 610,
Nylon 612, Nylon 6/66, Nylon 6/61
2. Nylon 6MXD (MXD indicates m-xylylenediamine component), nylon 66 / 6T (T indicates terephthalic acid component), nylon 6T / 6I (I indicates isophthalic acid component) and the like. These do not limit the scope of the invention. However, in the present invention, among these polyamide resins, nylon 6, nylon 66, nylon 6,
It is preferable to use nylon 11, nylon 12, nylon 6/66, nylon 66 / 6T, nylon 6T / 6I and the like. Particularly preferred are nylon 6, nylon 66, copolymers thereof, and mixtures thereof.

The number average molecular weight of the polyamide resin used in the present invention is not particularly limited and is usually 10,000.
What is in the range of -50000, preferably 13000-30000 can be optionally used. If the number average molecular weight of the polyamide resin is less than 10,000, the mechanical properties of the finally obtained polyamide resin composition will be poor, and if it is more than 50,000, the melt viscosity of the polyamide resin will be high, and moldability will be improved. It is not preferable in any case such as the deterioration of Further, when the number average molecular weight of the polyamide resin is more than 10,000 and less than 13,000, or the number average molecular weight of more than 30,000 and less than 50,000, the above-mentioned unfavorable phenomena may be exhibited.

The (B) modified polyphenylene ether polymer (sometimes abbreviated as m-PPE) used in the present invention is a modified polyphenylene ether polymer in which a specific modifier described below is modified in the molecular chain of the polyphenylene ether polymer. It is obtained by a graft reaction depending on the method. The polyphenylene ether polymer referred to here means the following general formula (1)

[0016]

[Chemical 1]

(Wherein R 1, R 2, R 3 and R 4 are hydrogen, halogen, an alkyl group, an alkoxy group, and a haloalkyl group and a haloalkoxy group having at least 2 carbon atoms between the halogen atom and the phenyl ring). ,
Further, it represents a monovalent substituent selected from those not containing a tertiary α-carbon, R1 to R4 may be the same or different from each other, and n is an integer representing the degree of polymerization. ) Is a polyphenylene ether (hereinafter abbreviated as "PPE"). These PPE may be one kind of the polymer represented by the above general formula or a copolymer in which two or more kinds are combined. Specific preferred examples of the homopolymer include:
In the above general formula, R1 and R4 are hydrogen atoms or an alkyl group having 1 to 4 carbon atoms, and R2 and R3 are PPE having an alkyl group having 1 to 4 carbon atoms, such as poly (2,6 -Dimethyl-1,4-phenylene)
Ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4)
-Phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-)
Dipropyl-1,4-phenylene) ether, poly (2
-Ethyl-6-propyl-1,4-phenylene) ether, poly (2,3,6-trimethyl-1,4-phenylene) ether, poly (2,3,6-triethyl-1,4)
-Phenylene) ether, poly (2,3-dimethyl-6)
-Ethyl-1,4-phenylene) ether, poly (2,2
3-dimethyl-6-propyl-1,4-phenylene) ether and the like can be mentioned. Further, the PPE copolymer is a copolymer containing a repeating unit of an alkyl trisubstituted phenol derivative such as poly (2,3,6-trimethyl-1,4-phenylene) ether in the above polyphenylene ether repeating unit. You can list coalescence.
In addition, styrene, α-methylstyrene,
A PPE copolymer obtained by modifying a styrene compound such as vinyltoluene or chlorostyrene may be used.
Further, as is well known in the art, a commercially available PPE polymer containing a styrene polymer may be used. Above P
Particularly preferred among PE homopolymers and PPE copolymers are poly (2,6) in which R1 is hydrogen or a methyl group, R2 and R3 are methyl groups, and R4 is hydrogen in the above general formula. -Dimethyl-1,4-
Poly (2,3,6-phenylene) ether, poly (2,3,6-trimethyl-1,4-phenylene) ether, and poly (2,6-dimethyl-1,4-phenylene) ether in the repeating unit of poly (2,3,6- There is a copolymer which partially contains a repeating unit of trimethyl-1,4-phenylene) ether.

In the present invention, 25 of these PPE polymers are used.
The intrinsic viscosity [η] measured in chloroform at 0 ° C was 0.
2-1.0 dl / g, preferably 0.3-0.7 dl /
It is preferably g. This intrinsic viscosity [η] is 0.2
If it is less than dl / g, the heat resistance improving effect and mechanical properties of the obtained polyamide resin composition are not sufficient. or,
When it is more than 1.0 dl / g, the moldability of the obtained polyamide resin composition is deteriorated. The modifier of the PPE polymer described above is an α, β-unsaturated carboxylic acid or its derivative. Specific examples of the α, β-unsaturated carboxylic acid include monobasic unsaturated compounds such as acrylic acid, methacrylic acid, methylmethacrylic acid, crotonic acid, isocrotonic acid, furanic acid, pentenoic acid, vinylacetic acid and angelic acid. Carboxylic acid, maleic acid, chloromaleic acid, fumaric acid,
Tetrahydrophthalic acid, itaconic acid, citraconic acid, endocis-bicyclo [2,2,1] hept-5-ene-
Examples thereof include dibasic unsaturated carboxylic acids such as 2,3-dicarboxylic acid (nadic acid) and tribasic unsaturated carboxylic acids such as citric acid and aconitic acid. Examples of the α, β-unsaturated carboxylic acid derivative include the above-mentioned monobasic, dibasic or tribasic unsaturated carboxylic acid derivatives such as acid halides, amides, imides, acid anhydrides and esters. Specific examples include maleenyl chloride, acrylamide, maleimide, N-phenylmaleimide, N-
Methyl maleimide, N-ethyl maleimide, maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, nadic anhydride, aconic anhydride, methyl acrylate, methyl methacrylate, monomethyl maleate, dimethyl maleate, itaconic acid Diethyl, dibutyl citraconic acid, glycidyl acrylate, glycidyl methacrylate, diglycidyl maleate and the like are used. Among these, preferred are acrylic acid, methacrylic acid, citric acid, maleic acid, maleic anhydride,
Itaconic anhydride and nadic acid anhydride are preferable, and maleic anhydride and citric acid are more preferable.

The concentration of the α, β-unsaturated carboxylic acid or its derivative as a modifier in the modified polyphenylene ether polymer is 0.05 to 1.5% by weight, preferably 0.1 to 1.3% by weight. %. If the concentration of the modifier is lower than the above range, the adhesion between the polyamide resin and the polyphenylene ether polymer phase is insufficient, and the resulting polyamide-based resin composition has an unstable structure and mechanical strength. It is not preferable because it lacks. or,
If it is higher than the above range, not only further compatibilizing effect cannot be expected, but also the melt flowability of the obtained polyamide resin composition is deteriorated and the moldability is impaired, which is not preferable. If the concentration of the modifier is more than 0.05% by weight and less than 0.1% by weight, or more than 1.3% by weight and less than 1.5% by weight, the above-mentioned unfavorable phenomena occur. I have something to do.

The method of modifying the PPE polymer is not particularly limited, and for example, a method of modifying the PPE polymer with the modifying agent in a molten state, or a method of modifying the solution in a solution, or In addition, various conventionally known methods such as a method of carrying out a modification reaction in a slurry state can be adopted. As a method of modifying the PPE polymer with the modifying agent in a molten state, specifically, the PPE polymer and the α, β-unsaturated carboxylic acid or the derivative thereof as the modifying agent are roll-milled. , Banbury mixer, extruder, etc.
Examples of the method include melt-kneading at the temperature of 10 seconds to 30 minutes to carry out a modification reaction. Further, as a method of modifying the PPE polymer with the modifier in a solution state, specifically, a solution obtained by dissolving the PPE polymer in a solvent such as benzene, toluene, xylene, decalin or tetralin is obtained. A method of adding the α, β-unsaturated carboxylic acid or the derivative thereof as the above-mentioned modifier and heating and stirring for the modification reaction can be mentioned. However, in the present invention, the method of modifying the PPE polymer and the α, β-unsaturated carboxylic acid or its derivative in the molten state by using the former extruder is the simplest and most efficient. When modifying the above PPE polymer,
If desired, a radical initiator such as an organic peroxide or an azo compound is allowed to be present, so that the PPE polymer and the α, β-unsaturated carboxylic acid of the modifier or a derivative thereof can be efficiently modified. Examples of the organic peroxide of the radical initiator include benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, cumene hydroperoxide, and 2,5-dimethyl-2. , 5-di-
(Tert-Butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy)
Hexin-3 and the like can be preferably mentioned. As the azo compound as the radical initiator, specifically, azobisisobutylnitrile, dimethylazoisobutyrate and the like can be preferably mentioned. These radical initiators are preferably used within the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the PPE polymer, but the type and amount of the radical initiator are also limited to the above. is not. The modified polyphenylene ether polymer used in the present invention is modified as described above as long as the content of the modifying agent in the component finally falls within the above-mentioned concentration range. It is also possible to use a mixture of the modified polyphenylene ether polymer and the unmodified polyphenylene ether polymer.

The (C) syndiotactic polystyrene polymer (abbreviated as SPS) used in the present invention is a styrene polymer having a syndiotactic structure. Here, the syndiotactic structure in the styrene-based polymer having a syndiotactic structure is a syndiotactic structure, that is, a phenyl group or a substitution which is a side chain with respect to the main chain formed from carbon-carbon bonds. It has a steric structure in which phenyl groups are alternately located in opposite directions, and its tacticity is quantified by a nuclear magnetic resonance method (13C-NMR method) using isotope carbon. Thirteen
The tacticity measured by the C-NMR method can be indicated by the abundance ratio of a plurality of continuous constitutional units, for example, diad in the case of 2, triad in the case of 3, and pentad in the case of 5. The styrene-based copolymer having a syndiotactic structure referred to in the present invention is usually 75% or more, preferably 85% or more in racemic dyad, or 30% or more in racemic pentad,
Preferably, polystyrene having a syndiotacticity of 50% or more, poly (alkylstyrene), poly (halogenated styrene), poly (halogenated alkylstyrene), poly (alkoxystyrene), poly (vinyl benzoate), these Of hydrogenated polymers and mixtures thereof, or copolymers containing these as the main components. Here, as poly (alkylstyrene), poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), poly (tert-butylstyrene), poly (phenylstyrene), poly (vinylnaphthalene), poly ( Vinyl styrene) and the like, and poly (halogenated styrene) includes poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene) and the like. Further, examples of the poly (halogenated alkylstyrene) include poly (chloromethylstyrene). Further, examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).

A particularly preferred styrene polymer is
Polystyrene, poly (p-methylstyrene), poly (m
-Methylstyrene), poly (p-tert-butylstyrene), poly (p-chlorostyrene), poly (m-chlorostyrene), poly (p-fluorostyrene), hydrogenated polystyrene and copolymers containing these structural units. Polymers may be mentioned. The styrene-based polymer may be used alone or in combination of two or more.

The styrene polymer is not particularly limited in molecular weight, but the weight average molecular weight is preferably 100.
It is at least 00, more preferably at least 50,000. Further, the molecular weight distribution is not limited to a wide or narrow range, and various kinds can be applied. Here, if the weight average molecular weight is less than 10,000, the thermal properties and mechanical properties of the obtained composition or molded product may be deteriorated, which is not preferable.

The styrenic polymer having such a syndiotactic structure can be prepared, for example, in an inert hydrocarbon solvent,
Alternatively, it can be produced by polymerizing a styrene-based monomer using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst in the absence of a solvent.
(JP-A-62-187708). Regarding poly (halogenated alkyl styrene), JP-A-1-469
No. 12, the above-mentioned hydrogenated polymer is disclosed in JP-A-1-17850.
It can be obtained by the method described in Japanese Patent Publication No. 5 or the like.

(D) Aromatic vinyl compound-aliphatic hydrocarbon copolymer used in the present invention ("SEPS, SEB
"S" may be abbreviated as "S") is a hydrogenated or non-hydrogenated styrene-isoprene copolymer or a hydrogenated or non-hydrogenated styrene-butadiene copolymer. As the hydrogenated or non-hydrogenated styrene / isoprene copolymer, a styrene / isoprene block copolymer or a hydrogenated product of a styrene / isoprene block copolymer is used. Further, as the hydrogenated or non-hydrogenated styrene-butadiene copolymer,
A styrene / butadiene block copolymer, a hydrogenated product of a styrene / butadiene copolymer or a hydrogenated product of a styrene / butadiene random copolymer is used. The hydrogenated styrene / isoprene copolymer or hydrogenated styrene / butadiene copolymer can be obtained by hydrogenation by a method known in the art, for example, the method shown in US Pat. No. 3,431,323. A commercially available product or a commercially available product can be appropriately selected and used.

In the present invention, the number average molecular weight of the above-mentioned aromatic vinyl compound-aliphatic hydrocarbon copolymer is 20.
In the range of 000 to 250,000, preferably 300.
The range is from 00 to 200,000. The number average molecular weight of the aromatic vinyl compound-aliphatic hydrocarbon copolymer is 20,000.
If less than, the compatibility with the modified polyphenylene ether polymer is insufficient, in the resulting polyamide resin composition, the target structure described later, that is, the secondary dispersed phase is included in the primary dispersed phase. Moreover, a composite particle type dispersion structure having a so-called core-shell structure cannot be obtained. When the number average molecular weight exceeds 250,000, the moldability and mechanical properties of the obtained polyamide resin composition are deteriorated. In the resulting polyamide resin composition, in order to ensure the prevention of the occurrence of these unfavorable phenomena, the component whose number average molecular weight is within the above-mentioned preferred range should be used. is there.

The styrene content of the aromatic vinyl compound-aliphatic hydrocarbon copolymer is such that the styrene monomer ratio in the polymer by infrared analysis is 5 to 80 wt%, preferably 10 to 70 wt%. These aromatic vinyl compound-aliphatic hydrocarbon copolymers containing styrene may be used alone or in combination of two or more. If the styrene monomer ratio is less than 5 wt%, the affinity for the shell phase is reduced, making it difficult to form a uniform core-shell structure and degrading various physical properties. A styrene monomer ratio of more than 80 wt% is not preferable because the flexibility of the core phase is lowered and the impact strength is lowered. When two or more kinds are mixed and used, the styrene content is 50-80.
A combination of the wt% aromatic vinyl compound-aliphatic hydrocarbon copolymer and the styrene content of 5 to 50 wt% aromatic vinyl compound-aliphatic hydrocarbon copolymer is preferable.
The ratio of the amount used at this time is 6 for the aromatic vinyl compound-aliphatic hydrocarbon copolymer having a styrene content of 50 wt% or more.
Aromatic vinyl compound-aliphatic hydrocarbon copolymer having a content of ˜87 wt% and a styrene content of 50 wt% or less is 94 to 13 w.
t%, preferably 13 to 75 wt% for the former and 87 for the latter.
~ 25 wt%.

The (E) ethylene / propylene copolymer (abbreviated as EPR) used in the present invention is obtained by copolymerizing at least two kinds of monomers selected from olefins described below, and It is an olefin copolymer having a tensile elastic modulus of 200 MPa or less at 23 ° C. measured according to D638. If the tensile modulus is higher than this range, the resulting resin composition may have low impact resistance and the effect of improving molding shrinkage and warpage during molding may not be sufficient. (E) As the olefin component unit constituting the ethylene / propylene copolymer, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1
-Heptene, 1-octene, 1-decene, dicyclopentadiene, ethylidene norbornene and the like can be exemplified, and two or more kinds of these are used. Of these olefin monomer units, ethylene and / or propylene are essential units, and the total amount of ethylene and / or propylene used is 50 to 100 mol%, preferably 7
It is 0 to 100 mol%. When the amount of ethylene and / or propylene used is less than this range, the affinity with (D) is insufficient, the structure of the structure becomes unstable, and the effect of improving impact resistance is reduced, and the mechanical properties obtained are reduced. Strength becomes low. In order to surely suppress the occurrence of these undesirable phenomena, it is preferable that the ethylene and / or propylene content be within the above-mentioned preferable range. Specific ethylene / propylene copolymers include ethylene / propylene
Propylene copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / ethylidene norbornene copolymer, ethylene / 1-butene copolymer, ethylene / 4-methyl-1-pentene copolymer,
An ethylene / olefin-based copolymer having a total usage of ethylene and / or propylene of 50 to 100 mol% such as an ethylene / 1-octene copolymer may be mentioned, but an ethylene / propylene copolymer is particularly preferably used. To be

The ethylene / propylene-based copolymer (E) used in the present invention is used as a mixture with the above-mentioned (D) aromatic vinyl compound-aliphatic hydrocarbon copolymer. Preferably, it is used as a mixture with an aromatic vinyl compound-aliphatic hydrocarbon copolymer having a styrene content of 50 wt% or more. The mixing ratio is 6 to 87 wt% of the (D) aromatic vinyl compound-aliphatic hydrocarbon copolymer, 94 to 13 wt% of the (E) ethylene / propylene copolymer, and preferably 13 to 75 wt% of the former. %, The latter is 87 to 25 wt%.

The polyamide resin composition of the present invention is
It is necessary to use (A) the polyamide resin as the matrix phase (continuous phase). When the polyamide resin (A) forms a continuous phase, the characteristics of the polyamide resin having excellent mechanical properties, heat resistance, chemical resistance, and moldability can be utilized. When the polyamide resin (A) does not form a continuous phase, the mechanical properties, chemical resistance, and moldability of the resulting resin composition are low, and the object of the present invention cannot be achieved. Further, in the polyamide resin composition of the present invention,
In the matrix phase of the polyamide resin (A), the modified polyphenylene ether polymer (B), the syndiotactic polystyrene polymer (C) and the aromatic vinyl compound-aliphatic hydrocarbon copolymer (D) are independently prepared. When dispersed, or to form a dispersed phase having a core-shell structure in which (D) is included in (B) and (C), (C)
When a part of the above forms an independent dispersed phase in the matrix of (A), satisfactory results cannot be obtained in mechanical properties such as impact resistance. Therefore, the dispersed phase formed by (B), (C) and (D) is the secondary dispersed phase (D).
It is indispensable to exhibit a composite particle dispersed structure having a so-called core-shell structure contained in (B) and (C) which are primary dispersed phases. That is, (B) the modified polyphenylene ether polymer and (C) the syndiotactic polystyrene polymer are compatible with each other, and the shell phase is (D) the aromatic vinyl compound-aliphatic hydrocarbon copolymer is the core phase. As a result, it is possible to obtain a polyamide resin composition having excellent rigidity, heat resistance, impact resistance, water resistance, etc., which satisfies the object of the present invention. In the present invention, any of (B), (C), and (D) forming the dispersed phase,
When (A) is modified with a polar group having reactivity or affinity with a polyamide resin, an unmodified polyphenylene ether polymer is used as (B) forming a dispersed phase, and (A), ( C), (D), and the modifying agent α,
When melt-kneaded with β-unsaturated carboxylic acid or its derivative, it forms a dispersed phase (B), (C) and (D).
Are dispersed individually in the matrix phase of the (A) polyamide resin, and the core-shell structure which is the object of the present invention cannot be obtained.

In the present invention, (A) the polyamide resin is 45 to 80 parts by weight, preferably 50 to 75 parts by weight, and (B) the modified polyphenylene ether polymer is 3 to 20 parts by weight.
5 parts by weight, preferably 5 to 15 parts by weight (C) of the syndiotactic polystyrene polymer is 5 parts by weight.
To 40 parts by weight, preferably 10 to 30 parts by weight (D), the aromatic vinyl compound-aliphatic hydrocarbon copolymer is 3 to 35 parts by weight, preferably 5 to 30 parts by weight ((A) + (B)). + (C) + (D) = 100 parts by weight), but (A) forms a matrix, (B) and (C) are compatible with each other to form a shell phase, and (D) is a core. In order to exhibit a solid dispersed phase having a core-shell type particle structure forming a phase, the following composition is preferable. (1) In the aromatic vinyl compound-aliphatic hydrocarbon copolymer (D), the hydrogenated or non-hydrogenated styrene / isoprene copolymer is 3 to 35 parts by weight, preferably 5 to 30 parts by weight. (2) In the (D) aromatic vinyl compound-aliphatic hydrocarbon copolymer, a block copolymer having a styrene content of 50 wt% or more is 6 to 87 wt%, preferably 13 to 75 wt%.
And a block copolymer 94 having a styrene content of 50 wt% or less
-13 wt%, preferably 87-25 wt%,
The amount used is 3-35 parts by weight, preferably 5-30 parts by weight. (3) (D) Aromatic vinyl compound-aliphatic hydrocarbon copolymer, hydrogenated or non-hydrogenated styrene / isoprene copolymer having a styrene content of 50 wt% or more, 6 to 87 wt%,
Preferably 13-75 wt% and styrene content 50 wt%
The following hydrogenated or non-hydrogenated styrene-isoprene copolymer 9
4 to 13 wt%, preferably 87 to 25 wt%, and the amount used is 3 to 35 parts by weight, preferably 5 to 30
Parts by weight. (4) (D) Aromatic vinyl compound-aliphatic hydrocarbon copolymer, hydrogenated or non-hydrogenated styrene / isoprene copolymer 6 to 87 wt% having a styrene content of 50 wt% or more,
Preferably 13-75 wt% and styrene content 50 wt%
The following hydrogenated or non-hydrogenated styrene-butadiene copolymer 9
4 to 13 wt%, preferably 87 to 25 wt%, and the amount used is 3 to 35 parts by weight, preferably 5 to 30
Parts by weight. (5) In the aromatic vinyl compound-aliphatic hydrocarbon copolymer (D), the block copolymer having a styrene content of 50 wt% or more is 6 to 87 wt%, preferably 13 to 75 wt%.
And (E) ethylene / propylene copolymer 94 to 13 wt.
%, Preferably 87 to 25 wt%, and the amount used is 3 to 35 parts by weight, preferably 5 to 30 parts by weight. (6) (D) Aromatic vinyl compound-aliphatic hydrocarbon copolymer, hydrogenated or non-hydrogenated styrene / isoprene copolymer having a styrene content of 50 wt% or more, 6 to 87 wt%,
Preferably 13 to 75 wt% and (E) ethylene / propylene copolymer 94 to 13 wt%, preferably 87 to 2
It is composed of 5 wt% and its amount is 3 to 35 parts by weight, preferably 5 to 30 parts by weight.

When the proportion of the polyamide resin (A) used exceeds 80 parts by weight, the water absorption of the resulting resin composition is insufficiently improved, resulting in an increase in dimensional change of the molded article due to moisture absorption and a decrease in elastic modulus. It is not preferable. On the other hand, if the proportion of (A) used is less than 45 parts by weight, the continuity of the polyamide resin phase will deteriorate and the mechanical strength, impact resistance, heat resistance and molding processability will deteriorate, which is not preferable.

When the proportion of the modified polyphenylene ether polymer (B) used is less than 3 parts by weight, the compatibility with the polyamide resin (A) and the syndiotactic polystyrene polymer (C) becomes poor and the desired core shell is obtained. While the composite particle dispersion structure having a structure can no longer be obtained,
Mechanical strength, impact resistance, rigidity, heat resistance, low water absorption, etc. of the obtained polyamide resin composition deteriorate, which is not preferable. On the other hand, when the content of (B) exceeds 20 parts by weight, the fluidity of the resulting resin composition during molding is deteriorated, which is not preferable.

When the proportion of the syndiotactic polystyrene-based polymer (C) used is less than 5 parts by weight, the rigidity and low water absorption are deteriorated, and when it exceeds 40 parts by weight, impact resistance and elongation are remarkably deteriorated. Not preferable.

When the proportion of the aromatic vinyl compound-aliphatic hydrocarbon copolymer (D) used is less than 3 parts by weight, the composite dispersion structure having a core-shell structure is insufficiently formed, resulting in low impact resistance and elongation. Therefore, a resin composition having well-balanced physical properties cannot be obtained. On the other hand, if the compounding ratio of (D) is more than 35 parts by weight, the mechanical strength and the rigidity are lowered, which is not suitable.

To the polyamide resin composition of the present invention, various types of reinforcing agents and fillers such as fibrous, powdery, flake-like or mat-like are added and blended within a range not impairing the molding processability and physical properties. can do. Specific examples of these reinforcing agents and fillers include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, basic magnesium sulfate fiber, boron fiber. , Stainless steel fibers, inorganic and metal fibers such as aluminum, titanium, copper, brass and magnesium, and organic fibers such as polyamide, polyester, polyacrylonitrile and cellulose, copper, iron, nickel, zinc, tin, stainless steel, aluminum, Metal powder of gold, silver, etc., fumed silica, aluminum silicate, calcium silicate, silicic acid, hydrous calcium silicate, hydrous aluminum silicate, glass beads, carbon black, quartz powder, talc, mica, titanium oxide, iron oxide, zinc oxide, Calcium carbonate,
Examples thereof include, but are not limited to, magnesium carbonate, magnesium oxide, calcium oxide, magnesium sulfate, potassium titanate, diatomaceous earth, and the like.
In the case of fibrous substances, the average fiber diameter is 0.1 to 30.
The one having a ratio of μm and fiber length / fiber diameter of 10 or more is preferably used. Further, these reinforcing agents and fillers may be surface-treated with a known silane coupling agent, titanate coupling agent or the like.

The amount of the reinforcing agent and the filler used is 1 to 3 parts by weight based on 100 parts by weight of the polyamide resin composition of the present invention.
The amount is 00 parts by weight, preferably 10 to 250 parts by weight. If the amount used is less than 1 part by weight, the effect of addition of the reinforcing agent and the additive is not recognized, and if it exceeds 300 parts by weight, moldability and mechanical properties of the polyamide resin composition are deteriorated. This is also not preferable. These reinforcing agents and fillers may be used alone or in admixture of two or more.

In the polyamide resin composition of the present invention, if necessary, hindered phenol, hydroquinone,
Antioxidants such as thioethers, phosphites, amines and their substitution products and copper compounds, heat stabilizers such as organotin, lead and metal soaps, UV stability such as resorcinol, salicylate, benzotriazole and benzophenone Agents, stearic acid and its salts, release agents such as stearyl alcohol, inorganic flame retardants such as red phosphorus, tin oxide, zirconium hydroxide, barium metaborate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide and hydrotalcite , Halogen-based, phosphoric acid ester-based, melamine or cyanuric acid-based organic flame retardants, anti-flame aids such as antimony trioxide, antistatic agents such as sodium dodecylbenzene sulfonate, polyalkylene glycol, alkyl betaines, etc., and crystallization acceleration Add additives such as agents, dyes, pigments, etc.
It is possible to add more than one kind.

The polyamide resin composition of the present invention contains an appropriate amount of polyethylene, polypropylene, an ethylene / vinyl acetate copolymer, within a range not impairing the object of the present invention.
Vinyl compound polymers such as ethylene / vinyl alcohol copolymer, polyvinyl acetate, polyvinyl chloride, poly 1-
Polyolefin such as butene and poly-4-methyl-1-pentene, thermoplastic elastomer such as polyamide elastomer, polyester elastomer, polyethylene terephthalate and polybutylene terephthalate, thermoplastic resin such as polycarbonate, polysulfone and polyphenylene sulfide, phenol resin, melamine resin Thermosetting resins such as urea resin, silicone resin, and epoxy resin can be added.

The method for producing the polyamide resin composition of the present invention is not particularly limited, and various methods known in the art can be used. For example, after the components (A), (B), (C) and (D) are pre-mixed at room temperature in the proportions used as described above, the temperature at which the melting of each of these components sufficiently progresses and does not decompose. As the above, a method of melt kneading at a temperature of 240 ° C. or higher, preferably 260 to 320 ° C. can be used. If the melt-kneading temperature exceeds 320 ° C., the crosslinking reaction and decomposition of the resin are likely to occur. The pre-mixing can be performed by using a high-speed rotary mixer such as a Henschel mixer and a low-speed rotary mixer such as a corn blender and a tumbler which are used for ordinary mixing. Further, the melt-kneading can be carried out by using an ordinary melt-kneading processing machine such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader and a mixing roll.

The polyamide resin composition of the present invention is
In addition to the four components of (A), (B), (C) and (D), a resin composition is prepared by adding a predetermined amount of the above-mentioned additive which is optionally added. Is not particularly limited, and these resin components and other components such as additives may be blended at the same time, or 2 to 3 resin components of these resin components may be blended in advance to form a mixture, A method may be adopted in which the resin component remaining thereafter is blended with other components such as additives. Alternatively, (A),
The resin components of (B), (C) and (D) may be first blended to produce a mixture, and then other components such as additives may be blended.

The polyamide resin composition of the present invention obtained as described above can be processed into molded articles for various uses by injection molding, compression molding, extrusion molding and the like.

[0043]

The present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded. Each component material (A) Polyamide resin PA6-1 used in Examples and Comparative Examples: Polyamide 6 having a number average molecular weight of 18,000
(UBE Nylon 1018B, manufactured by Ube Industries, Ltd.) PA66-1: Polyamide 6 having a number average molecular weight of 26000
6 (manufactured by Ube Industries, UBE nylon 2026B)

(B) Modified polyphenylene ether polymer m-PPE: As polyphenylene ether before modification,
A chloroform solution having a polymer concentration of 0.5 g / dl obtained by homopolymerizing 2,6-xylenol and having a relative viscosity of 0.45 at 25 ° C. was used. This polyphenylene ether and maleic anhydride are mixed at 280 ° C.
A maleic anhydride-modified polyphenylene ether was synthesized by melt-kneading at. This maleic anhydride-modified polyphenylene ether was obtained from the infrared absorption spectrum calibration curve prepared from a mixture of maleic anhydride and polyphenylene ether, and the reaction-added maleic anhydride concentration was determined to contain 0.2% by weight of maleic anhydride. It was something that was.

(C) Syndiotactic Polystyrene Polymer Syndiotactic polystyrene manufactured by Idemitsu Petrochemical Co., Ltd. was used. SPS-1: number average molecular weight by GPC is 150,000
Syndiotactic polystyrene (130A manufactured by Idemitsu Petrochemical Co., Ltd.)

(D) Aromatic vinyl compound-aliphatic hydrocarbon copolymer SEPS-1: hydrogenated styrene / isoprene block copolymer: number average molecular weight of 100,000, styrene occupied in the polymer by infrared analysis A hydrogenated styrene / isoprene triblock copolymer having a monomer ratio of 65% by weight was used.
(Young's modulus at 23 ° C. is 14000 kgf / cm ² ,
Kuraray Co., Ltd., Septon 2104) SEPS-2: Hydrogenated styrene / isoprene block copolymer ... The number average molecular weight is 100,000, and the monomer ratio of styrene in the polymer by infrared analysis is 30% by weight. A hydrogenated styrene / isoprene triblock copolymer was used.
(Young's modulus at 23 ° C. is 500 kgf / cm ² , Ltd.
Kuraray Co., Ltd., Septon 2002) SEPS-3: Hydrogenated styrene / isoprene block copolymer ... Hydrogenated styrene having a number average molecular weight of 50,000 and a monomer ratio of styrene in the polymer by infrared analysis of 13% by weight. -Isoprene triblock copolymer was used.
(SEPTON 2063, manufactured by Kuraray Co., Ltd.) SEBS-1: Hydrogenated styrene / butadiene block copolymer ... The number average molecular weight is 90,000, and the monomer ratio of styrene in the polymer by infrared analysis is 20% by weight. A hydrogenated styrene / butadiene triblock copolymer was used.
(Young's modulus at 23 ° C. is 100 kgf / cm ² , Asahi Kasei Corp., Tuftec H1052) SEBS-2: Hydrogenated styrene / butadiene block copolymer ... Monomer ratio of styrene in the polymer by infrared analysis Of hydrogenated styrene / butadiene triblock copolymer having a content of 29% by weight was used. (Clayton G1652 manufactured by Shell Chemical Co., Ltd.) SEBS-3: Hydrogenated styrene / butadiene block copolymer ... Number average molecular weight is 80,000, and monomer ratio of styrene in the polymer by infrared analysis is 30% by weight. The hydrogenated styrene / butadiene triblock copolymer which is
(Young's modulus at 23 ° C. is 500 kgf / cm ² , Asahi Kasei Corp., Tuftec H1041)

(E) Ethylene / propylene copolymer EPR: Propylene content 22% by weight, MFR
An ethylene / propylene copolymer having a (230 ° C., 2.16 kg) of 20 g / min was used. (JSR EP914P manufactured by Nippon Synthetic Rubber Co., Ltd.)

Examples 1 to 3 and Comparative Example 1 (A), (B), (C), and (D) were premixed at a usage rate shown in Table 1 using a tumbler. Next, this mixture is supplied to a TEX30 type twin-screw extruder manufactured by Japan Steel Works, and after melt-kneading at a cylinder temperature of 280 ° C., a molten resin extruded from a die of the extruder is cooled in a water tank, and then a strand cutter. Pelletized in.
The pellets of the polyamide resin composition thus obtained were vacuum dried at 80 ° C. for 24 hours, and then FANUC.
Using an AUTOSHOT-C30A type injection molding machine manufactured by
Cylinder temperature 280 ℃, mold temperature 80 ℃, injection speed 1
The test piece was molded under the condition of 00 mm / sec.
An injection molding machine NESTAL SG100 manufactured by Sumitomo Heavy Industries, Ltd. was used to create a test piece for DuPont impact, and a flat plate mold was used for 10
A flat plate of 0 mm × 100 mm × 3 mmt was formed and used as a test piece. Various physical properties of each of the test pieces molded in this manner were measured. The results are shown in Table 1. In each of the examples and comparative examples, each physical property was measured according to the following. DuPont impact strength: ASTM D2794 Using a 100 mm x 100 mm x 3 mmt flat plate-shaped test piece, the temperature was adjusted at -30 ° C for 24 hours in a low temperature constant temperature bath, and then measured with a DuPont impact tester. Izod impact strength: ASTM D256 Tensile strength and elongation: ASTM D638 Flexural strength and flexural modulus: ASTM D790 Load deflection temperature: ASTM D648 Injection pressure: Injection pressure at the time of molding a test piece by injection molding was measured. In addition, in each of the examples, as a result of observing the pellets with a transmission electron microscope photograph, it was confirmed that in the obtained polyamide resin composition, the dispersed phase had a core-shell type particle structure. The comparative example was not a core shell.

[0049]

[Table 1]

Examples 3 to 5 (A), (B), (C), and (D) were premixed in a tumbler at the use ratios shown in Table 2, respectively. Next, this mixture is supplied to a TEX30 type twin-screw extruder manufactured by Japan Steel Works, and after melt-kneading at a cylinder temperature of 280 ° C., a molten resin extruded from a die of the extruder is cooled in a water tank, and then a strand cutter. Pelletized in.
The pellets of the polyamide resin composition thus obtained were vacuum dried at 80 ° C. for 24 hours, and then FANUC.
Using an AUTOSHOT-C30A type injection molding machine manufactured by
Cylinder temperature 280 ℃, mold temperature 80 ℃, injection speed 1
The test piece was molded under the condition of 00 mm / sec.
An injection molding machine NESTAL SG100 manufactured by Sumitomo Heavy Industries, Ltd. was used to create a test piece for DuPont impact, and a flat plate mold was used for 10
A flat plate of 0 mm × 100 mm × 3 mmt was formed and used as a test piece. Various physical properties of each of the test pieces molded in this manner were measured. The results are shown in Table 2.

[0051]

[Table 2]

Examples 6 to 8 and Comparative Example 2 (A), (B), (C) and (D) were premixed by using a tumbler at the usage amounts shown in Table 3, respectively. Next, this mixture is supplied to a TEX30 type twin-screw extruder manufactured by Japan Steel Works, and after melt-kneading at a cylinder temperature of 280 ° C., a molten resin extruded from a die of the extruder is cooled in a water tank, and then a strand cutter. Pelletized in.
The pellets of the polyamide resin composition thus obtained were vacuum dried at 80 ° C. for 24 hours, and then FANUC.
Using an AUTOSHOT-C30A type injection molding machine manufactured by
Cylinder temperature 280 ℃, mold temperature 80 ℃, injection speed 1
The test piece was molded under the condition of 00 mm / sec.
An injection molding machine NESTAL SG100 manufactured by Sumitomo Heavy Industries, Ltd. was used to create a test piece for DuPont impact, and a flat plate mold was used for 10
A flat plate of 0 mm × 100 mm × 3 mmt was formed and used as a test piece. Various physical properties of each of the test pieces molded in this manner were measured. The results are shown in Table 3. As a result of observing the pellet with a transmission electron micrograph, it was confirmed that the polyamide-based resin composition obtained as a comparative example had a non-uniform dispersed phase and was not perfect as a core-shell type particle structure. Compared to the examples, the DuPont impact strength and Izod impact strength were inferior and the balance of other physical properties was poor.

[0053]

[Table 3]

Comparative Examples 3 to 6 (A), (B), (C) and (D) were premixed in a tumbler at the use ratios shown in Table 4, respectively. Next, this mixture is supplied to a TEX30 type twin-screw extruder manufactured by Japan Steel Works, and after melt-kneading at a cylinder temperature of 280 ° C., a molten resin extruded from a die of the extruder is cooled in a water tank, and then a strand cutter. Pelletized in.
The pellets of the polyamide resin composition thus obtained were vacuum dried at 80 ° C. for 24 hours, and then FANUC.
Using an AUTOSHOT-C30A type injection molding machine manufactured by
Cylinder temperature 280 ℃, mold temperature 80 ℃, injection speed 1
The test piece was molded under the condition of 00 mm / sec.
An injection molding machine NESTAL SG100 manufactured by Sumitomo Heavy Industries, Ltd. was used to create a test piece for DuPont impact, and a flat plate mold was used for 10
A flat plate of 0 mm × 100 mm × 3 mmt was formed and used as a test piece. Various physical properties of each of the test pieces molded in this manner were measured. The results are shown in Table 4. As a result of observing the pellet with a transmission electron micrograph, it was confirmed that the polyamide-based resin composition obtained as a comparative example had a non-uniform dispersed phase and was not perfect as a core-shell type particle structure. Compared to the examples, the DuPont impact strength and Izod impact strength were inferior and the balance of other physical properties was poor.

[0055]

[Table 4]

Examples 9 to 11 (A), (B), (C), and (D) were premixed in a tumbler at the use ratios shown in Table 5, respectively. Next, this mixture is supplied to a TEX30 type twin-screw extruder manufactured by Japan Steel Works, and after melt-kneading at a cylinder temperature of 280 ° C., a molten resin extruded from a die of the extruder is cooled in a water tank, and then a strand cutter. Pelletized in.
The pellets of the polyamide resin composition thus obtained were vacuum dried at 80 ° C. for 24 hours, and then FANUC.
Using an AUTOSHOT-C30A type injection molding machine manufactured by
Cylinder temperature 280 ℃, mold temperature 80 ℃, injection speed 1
The test piece was molded under the condition of 00 mm / sec.
An injection molding machine NESTAL SG100 manufactured by Sumitomo Heavy Industries, Ltd. was used to create a test piece for DuPont impact, and a flat plate mold was used for 10
A flat plate of 0 mm × 100 mm × 3 mmt was formed and used as a test piece. Various physical properties of each of the test pieces molded in this manner were measured. The results are shown in Table 5. As a result of observing the pellet with a transmission electron microscope photograph, it was confirmed that the dispersed phase of the polyamide resin composition had a core-shell type particle structure.

[0057]

[Table 5]

Examples 12 to 14 (A), (B), (C), and (D) were premixed in a tumbler at the use ratios shown in Table 6, respectively. Next, this mixture is supplied to a TEX30 type twin-screw extruder manufactured by Japan Steel Works, and after melt-kneading at a cylinder temperature of 280 ° C., a molten resin extruded from a die of the extruder is cooled in a water tank, and then a strand cutter. Pelletized in.
The pellets of the polyamide resin composition thus obtained were vacuum dried at 80 ° C. for 24 hours, and then FANUC.
Using an AUTOSHOT-C30A type injection molding machine manufactured by
Cylinder temperature 280 ℃, mold temperature 80 ℃, injection speed 1
The test piece was molded under the condition of 00 mm / sec.
An injection molding machine NESTAL SG100 manufactured by Sumitomo Heavy Industries, Ltd. was used to create a test piece for DuPont impact, and a flat plate mold was used for 10
A flat plate of 0 mm × 100 mm × 3 mmt was formed and used as a test piece. Various physical properties of each of the test pieces molded in this manner were measured. The results are shown in Table 6. As a result of observing the pellet with a transmission electron microscope photograph, it was confirmed that the dispersed phase of the polyamide resin composition had a core-shell type particle structure.

[0059]

[Table 6]

Comparative Examples 7 and 8 (A), (B), (C), and (D) were premixed at a usage ratio shown in Table 7 by using a tumbler. Next, this mixture is supplied to a TEX30 type twin-screw extruder manufactured by Japan Steel Works, and after melt-kneading at a cylinder temperature of 280 ° C., a molten resin extruded from a die of the extruder is cooled in a water tank, and then a strand cutter. Pelletized in.
The pellets of the polyamide resin composition thus obtained were vacuum dried at 80 ° C. for 24 hours, and then FANUC.
Using an AUTOSHOT-C30A type injection molding machine manufactured by
Cylinder temperature 280 ℃, mold temperature 80 ℃, injection speed 1
The test piece was molded under the condition of 00 mm / sec.
An injection molding machine NESTAL SG100 manufactured by Sumitomo Heavy Industries, Ltd. was used to create a test piece for DuPont impact, and a flat plate mold was used for 10
A flat plate of 0 mm × 100 mm × 3 mmt was formed and used as a test piece. Various physical properties of each of the test pieces molded in this manner were measured. The results are shown in Table 7. As a result of observing the pellet with a transmission electron micrograph, it was confirmed that the polyamide-based resin composition obtained as a comparative example had a non-uniform dispersed phase and was not perfect as a core-shell type particle structure. Compared to the examples, the DuPont impact strength and Izod impact strength were inferior and the balance of other physical properties was poor.

[0061]

[Table 7]

Comparative Examples 9, 10 (A), (B), (C), and (D) were premixed in a tumbler at the use ratios shown in Table 8, respectively. Next, this mixture is supplied to a TEX30 type twin-screw extruder manufactured by Japan Steel Works, and after melt-kneading at a cylinder temperature of 280 ° C., a molten resin extruded from a die of the extruder is cooled in a water tank, and then a strand cutter. Pelletized in.
The pellets of the polyamide resin composition thus obtained were vacuum dried at 80 ° C. for 24 hours, and then FANUC.
Using an AUTOSHOT-C30A type injection molding machine manufactured by
Cylinder temperature 280 ℃, mold temperature 80 ℃, injection speed 1
The test piece was molded under the condition of 00 mm / sec.
An injection molding machine NESTAL SG100 manufactured by Sumitomo Heavy Industries, Ltd. was used to create a test piece for DuPont impact, and a flat plate mold was used for 10
A flat plate of 0 mm × 100 mm × 3 mmt was formed and used as a test piece. Various physical properties of each of the test pieces molded in this manner were measured. The results are shown in Table 8. As a result of observing the pellet with a transmission electron micrograph, it was confirmed that the polyamide-based resin composition obtained as a comparative example had a non-uniform dispersed phase and was not perfect as a core-shell type particle structure. Compared to the examples, the DuPont impact strength and Izod impact strength were inferior and the balance of other physical properties was poor.

[0063]

[Table 8]

Example 15 and Comparative Example 11 (A), (B), (C) and (D) were premixed using a tumbler at the use ratios shown in Table 9, respectively. Next, this mixture is supplied to a TEX30 type twin-screw extruder manufactured by Japan Steel Works, and after melt-kneading at a cylinder temperature of 280 ° C., a molten resin extruded from a die of the extruder is cooled in a water tank, and then a strand cutter. Pelletized in.
The pellets of the polyamide resin composition thus obtained were vacuum dried at 80 ° C. for 24 hours, and then FANUC.
Using an AUTOSHOT-C30A type injection molding machine manufactured by
Cylinder temperature 280 ℃, mold temperature 80 ℃, injection speed 1
The test piece was molded under the condition of 00 mm / sec.
An injection molding machine NESTAL SG100 manufactured by Sumitomo Heavy Industries, Ltd. was used to create a test piece for DuPont impact, and a flat plate mold was used for 10
A flat plate of 0 mm × 100 mm × 3 mmt was formed and used as a test piece. Various physical properties of each of the test pieces molded in this manner were measured. The results are shown in Table 9. As a result of observing the pellets with a transmission electron micrograph, it was confirmed that the polyamide resin composition obtained as a comparative example had a non-uniform dispersed phase and did not have a core-shell type particle structure. Compared to the examples, the DuPont impact strength and Izod impact strength were inferior and the balance of other physical properties was poor.

[0065]

[Table 9]

[0066]

According to the present invention, various mechanical properties (especially DuPont impact value, Izod impact value, elongation, strength, elastic modulus), solvent resistance, low water absorption, dimensional stability, heat resistance, It is possible to provide a lightweight polyamide-based resin composition suitable for molding processability, the polyamide-based resin composition of the present invention,
It can be used in a wide range of fields such as electric / electronic parts, automobile parts, and mechanical parts.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4J002 BC033 BP014 CH072 CL011                       CL031 CL051 GM00 GN00                       GQ00

Claims (4)

[Claims] 1. (A) Polyamide resin 45 to 80 parts by weight, (B) Modified polyphenylene ether polymer 3 to 20 parts by weight, (C) Syndiotactic polystyrene polymer 5 to 40 parts by weight, (D) Aroma Group vinyl compound-aliphatic hydrocarbon copolymer 3 to 35 parts by weight (however, (A) + (B) + (C) + (D) = 100 parts by weight), and (A) forms a matrix. ,
(B) and (C) are compatible with each other to form a shell phase,
(D) represents a dispersed phase having a core-shell type particle structure that forms a core phase, and a polyamide resin composition. 2. The polyamide resin composition according to claim 1, wherein the aromatic vinyl compound-aliphatic hydrocarbon copolymer (D) is a hydrogenated or non-hydrogenated styrene / isoprene copolymer. 3. An aromatic vinyl compound-aliphatic hydrocarbon copolymer (D) comprising 6 to 87 wt% of an aromatic vinyl compound-aliphatic hydrocarbon copolymer having a styrene content of 50 wt% or more and styrene content of 50 wt% or less. 2. The polyamide resin composition according to claim 1, which comprises 94 to 13 wt% of the aromatic vinyl compound-aliphatic hydrocarbon copolymer. 4. An aromatic vinyl compound-aliphatic hydrocarbon copolymer (D) comprising 6 to 87 wt% of an aromatic vinyl compound-aliphatic hydrocarbon copolymer having a styrene content of 50 wt% or more and (E) ethylene. Propylene copolymer 94 to 13 wt
%, The polyamide resin composition according to claim 1.