JP2003049064A - Resin composition with excellent impact resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which can achieve high impact resistance, particularly dart impact characteristics, and has both heat resistance and fluidity. SOLUTION: (A) Polyphenylene ether resin 1
(C) 100 parts by weight of a resin component comprising 99 to 1 part by weight of a polymer having a carboxyl group at the terminal, and (C) a block copolymer or aromatic vinyl compound of an aromatic vinyl compound and a conjugated diene compound And a block copolymer of an acrylic vinyl compound and a functionalized compound, wherein the functionalized compound contains 0.05 to 30 parts by weight of a polymer, and (D) a compound containing an I-, II- or III-valent metal element. 001 to 10 parts by weight of a resin composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition which can achieve impact resistance, especially dirt impact characteristics at a high level, and has both heat resistance and fluidity.

[0002]

2. Description of the Related Art Generally, polyphenylene ether is a resin having excellent properties such as heat resistance, hot water resistance, dimensional stability, and mechanical and electrical properties. On the other hand, its moldability is high because of its high melt viscosity. Bad, poor chemical resistance,
It has drawbacks such as low impact resistance. In order to improve such drawbacks of polyphenylene ether, alloying of polyphenylene ether with other resin or modification of polyphenylene ether has been conventionally performed.

For example, in order to improve the impact resistance of polyphenylene ether, high-impact polystyrene, aromatic vinyl compound-conjugated diene compound block copolymer,
Aromatic vinyl compound-a method of adding a hydrogenated product of a conjugated diene compound block copolymer has been taken,
All of them reduce the heat resistance of polyphenylene ether, and the balance between heat resistance and impact resistance was not sufficient. Further, in order to improve the fluidity of polyphenylene ether, a method of alloying with polystyrene, liquid crystal polyester, etc. has been taken, but impact resistance, especially dart impact characteristics, is lowered, and the balance between fluidity and impact resistance is reduced. Wasn't enough.

As a technique for improving the thermal stability of polyphenylene ether, Japanese Patent Publication No. 56-22909 discloses that:
It has been proposed to add an alkanolamine, an inorganic sulfide and a metal oxide to polyphenylene ether, but the balance between impact resistance and heat resistance was not sufficient. Further, JP-A-5-171016 proposes a polyester resin and a polyphenylene ether resin composition which are excellent in heat resistance, impact strength, etc., but is insufficient in fluidity and impact resistance, particularly dirt impact resistance. There wasn't.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a resin composition which can achieve impact resistance, especially dirt impact characteristics at a high level, and which has both heat resistance and fluidity.

[0006]

[Means for Solving the Problems] As a result of repeated studies to achieve the above object, a polyphenylene ether resin, a polymer having a carboxyl group at a terminal, a copolymer of a specific aromatic vinyl compound and a conjugated diene compound, or an aromatic compound Achievement of impact resistance, especially dirt impact properties, at a high level by blending a polymer in which a copolymer of group vinyl and an acrylic vinyl compound is functionalized with a functionalized compound and a specific metal-containing compound in a specific ratio It was found that a resin composition having both heat resistance and fluidity can be obtained.

That is, the present invention relates to 1. (A) 1 to 99 parts by weight of a polyphenylene ether resin and (B) a polymer 99 having a carboxyl group at the end.
To 1 part by weight of a resin component, (C) a copolymer of an aromatic vinyl compound and a conjugated diene compound or a block copolymer of an aromatic vinyl compound and an acrylic vinyl compound is functionalized with a functionalized compound. 0.001 containing 0.05 to 30 parts by weight of the polymer and (D) I-valent, II-valent or III-valent metal element
A resin composition comprising 10 to 10 parts by weight,

2. The component (B) is at least one selected from polyamide-based resins, polyester-based resins and liquid crystal polyester-based resins.
2. The resin composition described in 3. (B) component is a liquid crystal polyester-based resin, wherein the resin composition according to the above 1,

4. The component (C) is a polymer in which a block copolymer of an aromatic vinyl compound and a conjugated diene compound is partially hydrogenated and functionalized with a functionalized compound, according to any one of the above 1 to 3. 4. The resin composition of The functionalized compound in the component (C) is a compound modified with an α, β-unsaturated carboxylic acid or an α, β-unsaturated carboxylic acid anhydride.
4. The resin composition according to any one of 4 above,

6. The functionalized compound in the component (C) is
6. The resin composition according to any one of 1 to 4 above, which is modified with maleic acid or maleic anhydride. (D) component is a zinc compound, Resin composition in any one of said 1-6 characterized by the above-mentioned.

8. 7. The resin composition according to any one of 1 to 6 above, wherein the component (D) is zinc oxide. Resin component 100 comprising component (A) and component (B)
Further, (E) an inorganic filler is added in an amount of 0.1 to 10 parts by weight.
The resin composition according to any one of 1 to 8 above, characterized in that 0 part by weight is added.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. (A) Polyphenylene ether resin means a repeating unit structure of (Formula 1)

[0013]

[Chemical 1]

(R ₁ and R ₄ are each independently hydrogen,
Represents primary or secondary lower alkyl, phenyl, aminoalkyl, hydrocarbon oxy. R ₂ and R ₃ each independently represent hydrogen, primary or secondary lower alkyl, or phenyl. ), And reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.)
Is a homopolymer and / or a copolymer in the range of 0.15 to 1.0 dl / g. A preferred reduced viscosity is in the range of 0.20 to 0.70 dl / g, most preferably in the range of 0.40 to 0.60.

Specific examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene ether) and poly (2-methyl-6-ethyl).
1,4-phenylene ether), poly (2-methyl-6)
-Phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether),
In addition, polyphenylene ether copolymer such as a copolymer of 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol and 2-methyl-6-butylphenol). There is also a combination. Among them, poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,
A copolymer with 3,6-trimethylphenol is preferable, and poly (2,6-dimethyl-1,4-phenylene ether) is more preferable.

As an example of the method for producing (A) polyphenylene ether used in the present invention, US Pat.
There is a method of oxidatively polymerizing 2,6-xylenol using a complex of cuprous salt and amine described in No. 4 as a catalyst. U.S. Pat. Nos. 3,306,875 and 325.
The methods described in the specifications of 7357 and 3257358, JP-B-52-17880 and JP-A-50-51197 and 63-152628 are also used as the method for producing (A) polyphenylene ether. preferable. The polyphenylene ether resin (A) of the present invention may be used as a powder after the polymerization step, or may be used in an N ₂ gas atmosphere or a non-N ₂ gas atmosphere under a devolatilizing or non-volatilizing state using an extruder or the like. It may be pelletized by melt-kneading under devolatilization.

The polyphenylene ether resin (A) of the present invention also includes polyphenylene ether functionalized with various dienophile compounds. Examples of various dienophile compounds include maleic anhydride, maleic acid, fumaric acid, phenylmaleimide, itaconic acid, acrylic acid, methacrylic acid, methyl arylate, methyl methacrylate, glycidyl acrylate, glycidyl methacrylate, stearyl acrylate, and styrene. Can be mentioned. As a method of functionalizing with these dienophile compounds, an extruder or the like may be used in the presence or absence of a radical generator, and the functionalization may be performed in a molten state with or without devolatilization. Alternatively, it may be functionalized in the non-molten state, that is, in the temperature range from room temperature to the melting point, in the presence or absence of a radical generator. At this time, the melting point of the polyphenylene ether is defined by the peak top temperature of the peak observed in the temperature-heat flow rate graph obtained when the temperature is raised at 20 ° C./min in the measurement with a differential scanning calorimeter (DSC). When there are multiple peak top temperatures, it is defined as the highest temperature among them.

The polyphenylene ether resin (A) of the present invention has a number average molecular weight of 1,000 to 100,
000 is preferable. A more preferred range is about 6,000.
It is 0 to 60,000. Particularly preferred as the use of engineering resin is about 10,000 to 30,000.
It is 0. The number average molecular weight of the present invention is a polystyrene equivalent number average molecular weight determined by gel permeation chromatography using a calibration curve of standard polystyrene.

The polyphenylene ether resin (A) of the present invention may contain an aromatic vinyl polymer as long as the characteristics of the present invention are not impaired. Examples of the aromatic vinyl-based polymer include atactic polystyrene, syndiotactic polystyrene, high-impact polystyrene, and acrylonitrile-styrene copolymer. When a mixture of a polyphenylene ether resin and an aromatic vinyl polymer is used, the polyphenylene ether resin is 70 w based on the total amount of the polyphenylene ether resin and the aromatic vinyl polymer from the viewpoint of heat resistance.
It is at least t%, preferably at least 80 wt%, more preferably at least 90 wt%.

A preferred example of the polymer having a carboxyl group at the terminal (B) of the present invention is a polyamide resin,
Examples thereof include polyester resins and liquid crystal polyester resins. Of these, liquid crystal polyester resins are particularly preferable, and thermotropic liquid crystal polyester is most preferable. Known liquid crystal polyester resins can be used. For example, thermotropic liquid crystal polyester mainly containing p-hydroxybenzoic acid and polyethylene terephthalate, p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid are mainly used. Examples thereof include thermotropic liquid crystal polyester having a structural unit, p-hydroxybenzoic acid, and thermotropic liquid crystal polyester having 4,4′-dihydroxybiphenyl and terephthalic acid as a main structural unit, with no particular limitation.

As the liquid crystal polyester used in the present invention, those comprising the following structural units (a) and (b) and, if necessary, (c) and / or (d) are preferably used.

[0022]

[Chemical 2]

[0023]

[Chemical 3]

[0024]

[Chemical 4]

[0025]

[Chemical 5]

Here, the structural units (a) and (b) are a structural unit of polyester produced from p-hydroxybenzoic acid and a structural unit produced from 2-hydroxy-6-naphthoic acid, respectively. By using the structural units (a) and (b), it is possible to obtain the thermoplastic resin composition of the present invention which is excellent in balance of mechanical properties such as heat resistance, fluidity and rigidity. X in the above structural units (C) and (D)
Can be arbitrarily selected from the following (formula 2) or two or more can be selected.

[0027]

[Chemical 6]

In the structural formula (C), preferred are structural units formed from ethylene glycol, hydroquinone, 4,4'-dihydroxybiphenyl, 2,6-dihydroxynaphthalene and bisphenol A, respectively.
More preferred are ethylene glycol, 4,4'-
Dihydroxybiphenyl and hydroquinone are preferable, and ethylene glycol and 4,4'-dihydroxybiphenyl are particularly preferable. In the structural formula (d), structural units formed from terephthalic acid, isophthalic acid, and 2,6-dicarboxynaphthalene are preferable, and terephthalic acid and isophthalic acid are more preferable.

In the structural formula (c) and the structural formula (d), at least one kind or two or more kinds of the structural units listed above can be used in combination. Specifically, in the case of using two or more kinds in combination, in the structural formula (c), 1) a structural unit generated from ethylene glycol / a structural unit generated from hydroquinone, 2) a structural unit generated from ethylene glycol / 4, 4 Structural unit formed from ′ -dihydroxybiphenyl, 3) Structural unit formed from hydroquinone /
Structural units formed from 4,4'-dihydroxybiphenyl and the like can be mentioned.

Further, in the structural formula (d), 1) a structural unit produced from terephthalic acid / a structural unit produced from isophthalic acid, 2) a structural unit produced from terephthalic acid / 2, produced from 2,6-dicarboxynaphthalene Examples of the structural unit include: Here, the amount of terephthalic acid in the two components is preferably 40% by weight or more, more preferably 60% by weight or more, and particularly preferably 80% by weight or more. When the amount of terephthalic acid is 40% by weight or more in the two components, the resin composition has relatively good fluidity and heat resistance. The division of use of the structural units (a), (b), (c) and (d) in the liquid crystal polyester (B) component is not particularly limited. However, the structural units (C) and (D) are basically almost equimolar amounts.

The structural unit (e) consisting of the structural units (c) and (d) can also be used as the structural unit in the component (B). Specifically, 1) a structural unit formed from ethylene glycol and terephthalic acid, 2) a structural unit formed from hydroquinone and terephthalic acid, 3) 4,
Structural units formed from 4'-dihydroxybiphenyl and terephthalic acid, 4) Structural units formed from 4,4'-dihydroxybiphenyl and isophthalic acid, 5) Structural units formed from bisphenol A and terephthalic acid, and the like. it can.

[0032]

[Chemical 7]

A polymer obtained by functionalizing a block copolymer of an aromatic vinyl compound and a conjugated diene compound or a copolymer of an aromatic vinyl compound and an acrylic vinyl compound, which is the component (C) of the present invention, with a functionalizing compound. Will be described below. First, here, the block copolymer of an aromatic vinyl compound and a conjugated diene compound means a block copolymer composed of a polymer block segment mainly composed of an aromatic vinyl compound and a polymer block segment mainly composed of a conjugated diene compound. It is a polymer. Further, a copolymer of an aromatic vinyl compound and an acrylic vinyl compound is a block copolymer composed of a polymer block segment mainly containing an aromatic vinyl compound and a polymer block segment mainly containing an acrylic vinyl compound. Is.

Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene and pt.
At least one selected from ert-butyl styrene, divinyl benzene, p-methyl styrene, 1,1-diphenyl styrene and the like can be selected, and styrene is preferable. Then, specific examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene,
2,3-dimethyl-1,3-butadiene, piperylene,
3-butyl-1,3-octadiene, phenyl-1,3
-At least one selected from butadiene and the like can be selected, and among them, butadiene, isoprene, and combinations thereof are preferable. Specific examples of the acrylic vinyl compound include methyl methacrylate, methacrylic acid, methyl acrylate, acrylic acid and the like.

Further, the functionalized compound in the component (C) is a compound having an unsaturated bond, and a compound having a double bond is particularly preferable. Specific examples include maleic anhydride, maleic acid, fumaric acid, phenylmaleimide, itaconic acid, acrylic acid, methacrylic acid, methyl arylate, methyl methacrylate, glycidyl acrylate, glycidyl methacrylate, stearyl acrylate, styrene and the like. Further, α, β-unsaturated carboxylic acid or α, β-unsaturated carboxylic acid anhydride may be mentioned. That is, more specific examples include maleic acid, fumaric acid, maleic anhydride and the like. Maleic anhydride is particularly preferably used.

As a method of functionalizing the block copolymer of the aromatic vinyl compound and the conjugated diene compound or the copolymer of the aromatic vinyl compound and the acrylic vinyl compound with these functionalized compounds, an extruder or the like is used. In the presence or absence of a radical initiator, melt kneading may be performed, or the reaction may be performed in a solution.

Further, the component (C) is a polymer in which a block copolymer of an aromatic vinyl compound and a conjugated diene compound is partially hydrogenated by hydrogenation and functionalized by the above functionalized compound, It is preferable from the viewpoint of heat deterioration resistance. Furthermore, its hydrogenation rate is 5-100%
Are preferred. Further, from the viewpoint of thermal stability, a hydrogenation rate of 50% or more is more preferable. Structural characteristics of the partially hydrogenated block copolymer are described in JP-A-61-161.
One type or two or more types can be used in combination as long as they satisfy the requirements described in detail in JP-A-34049. For example,
Specific examples of this partially hydrogenated block copolymer include those sold under the name "Tuftec (registered trademark)" by Asahi Kasei Corporation. Further, specific examples of the polymers functionalized with these partially hydrogenated block copolymers by a functionalizing compound include those sold by Asahi Kasei Corporation under the name of "Tuftec M series (registered trademark)". Can be mentioned. The functionalization rate (defined by the weight fraction of the functionalized compound and the partially hydrogenated block copolymer) is preferably 0.1 to 10%, more preferably 0.3 to 5%. If this functionalization rate is less than 0.1%, the effect of improving the dart impact is not sufficient, and 10%
If it is more than the above range, heat resistance is deteriorated, which is not preferable.

(D) I value, II value or III of the present invention
The compound containing a valent metal element is an inorganic compound or an organic compound containing a metal. The component (D) of the present invention is essentially a compound containing a metal element as a main constituent component. The component (D) of the present invention includes Li, Na, K, Zn,
Cd, Sn, Cu, Ni, Pd, Co, Fe, Ru, M
A compound containing any one of n, Pb, Mg, Ca, Sr, Ba and Al is preferable. Furthermore, (D)
The component is a compound containing a metal element having a valence of I, II or III, ZnO and / or ZnS and / or CdO and / or CdS and / or SnO.
And / or SnS and / or zinc stearate and / or zinc acetate and / or MgO are preferred. Further, the component (D) is more preferably a zinc compound. Furthermore, zinc oxide is extremely preferable.

The inorganic filler (E) of the present invention means glass fiber, carbon fiber, whiskers, mica, talc, carbon black, titanium oxide, calcium carbonate, potassium titanate, wollastonite, conductive metal fibers, conductive materials. Carbon black, etc. Of these, glass fiber is preferable. The fibrous filler such as glass fiber may be coated or bundled with a thermoplastic resin such as ethylene / vinyl acetate copolymer or a thermosetting resin such as epoxy resin.

The amount of the (A) polyphenylene ether resin used in the present invention is 1 to 99 parts by weight, preferably 10 to 95 parts by weight, and more preferably 40 to 95 parts by weight. If the blending amount is more than 99 parts by weight, the fluidity will be significantly reduced. If the amount is less than 1 part by weight, sufficient impact resistance, especially dirt impact resistance, and appearance cannot be obtained. The amount of the polymer having a carboxyl group at the terminal (B) in the present invention is 99 to 1 part by weight, preferably 90 to 5 parts by weight, and more preferably 60 to 5 parts by weight. If the content is more than 99 parts by weight, sufficient impact resistance, especially dirt impact resistance cannot be obtained. This compounded amount is 1
If it is less than the weight part, sufficient fluidity cannot be obtained.

The block copolymer (C) of the aromatic vinyl compound and the conjugated diene compound or the copolymer of the aromatic vinyl compound and the acrylic vinyl compound in the present invention is
The amount of the polymer functionalized with the functionalized compound is
With respect to 100 parts by weight of the total of the components (A) and (B),
The amount is 0.05 to 30 parts by weight, preferably 0.5 to 15 parts by weight. If the amount is more than 30 parts by weight, the heat resistance is lowered, and if it is less than 0.05 parts by weight, sufficient impact resistance, particularly dirt impact resistance cannot be obtained.

The compounding amount of the compound (D) containing an I-valent, II-valent or III-valent metal element in the present invention is
With respect to 100 parts by weight of the total of the components (A) and (B),
0.001 to 10 parts by weight, more preferably 0.05
~ 5 parts by weight. If the amount is less than 0.001 part by weight, the impact resistance, especially the dart impact resistance will be reduced, and if it is more than 5 parts by weight, the appearance will be poor. The addition amount of the inorganic filler of the component (E) in the present invention is 0.1 to 100 parts by weight, preferably 1 to 80 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). It is preferably 5 to 50 parts by weight. If the addition amount is more than 100 parts by weight, the appearance and the fluidity of the molded product are deteriorated. If the amount added is less than 0.1 parts by weight, it is difficult to obtain sufficient rigidity.

In the present invention, in addition to the above-mentioned components, other optional components such as an antioxidant and a flame retardant (organic phosphate ester-based compound) may be added as required within the range not impairing the characteristics and effects of the present invention. , Inorganic phosphorus compounds, aromatic halogen flame retardants, etc.), elastomers (ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene / propylene / non-conjugated diene copolymers, ethylene / ethyl acrylate copolymers) Polymer, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene / propylene-g-maleic anhydride copolymer, olefin copolymer such as ABS, polyester polyether elastomer , Polyester polyester elastomer, unmodified aromatic vinyl block copolymer, Unmodified partially hydrogenated aromatic vinyl block copolymer, plasticizer (oil, low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), flame retardant aid, weather (light) resistance improver ,
Nucleating agents, slip agents, various coloring agents, release agents, etc. may be added.

The resin composition of the present invention can be manufactured by various methods. For example, a heat-melting and kneading method using a single-screw extruder, a twin-screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer and the like can be mentioned. Among them, the melt-kneading method using a twin-screw extruder is most preferable. The melt-kneading temperature at this time is not particularly limited, but it can usually be arbitrarily selected from 150 to 350 ° C. The resin composition of the present invention thus obtained, various conventional methods, for example, injection molding,
It can be molded as a molded body of various parts by extrusion molding or hollow molding. These various parts are suitable for automobile parts and electronic / electric parts, for example.

As described above, in the present invention, (A)
(C) A block copolymer of an aromatic vinyl compound and a conjugated diene compound or a copolymer of an aromatic vinyl compound and an acryl vinyl compound is functionalized with a functionalized compound in a resin composition of the component and the component (B). The resin composition obtained by adding a small amount of the polymerized polymer and further adding a small amount of (D) a compound containing an I-valent, II-valent or III-valent metal element is a resin composition containing no component (D), or It has been found that the impact resistance, especially the dirt impact resistance, is significantly improved as compared with the case where the partially hydrogenated block copolymer corresponding to the component (C) is not functionalized. The present invention will be described below.
A description will be given based on examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

(Production Example 1) Polyphenylene ether (P
Production Example of Poly (2,6-dimethyl-1,4-phenylene ether) having a reduced viscosity of 0.43 obtained by oxidative polymerization of 2,6-dimethylphenol, and differential thermal scanning Temperature obtained when the calorimeter (DSC) is measured and the temperature is raised at 20 ° C./min.
A single peak was shown when the peak top temperature of the heat flow graph was the melting point, and the melting point was 250 ° C.

(Production Example 2) Liquid crystalline polyester (LCP-
1) may be abbreviated as 1) in a nitrogen atmosphere, p-hydroxybenzoic acid, 2-
Hydroxy-6-naphthoic acid and acetic anhydride were charged, heated and melted, and polycondensed to obtain a liquid crystal polyester (LCP-1) having the following theoretical structural formula. In addition, the component ratio of a composition represents a molar ratio.

[0048]

[Chemical 8]

(Production Example 3) Liquid crystalline polyester (LCP-
2, which may be abbreviated as 2), p-hydroxybenzoic acid, polyethylene terephthalate, and acetic anhydride are charged under a nitrogen atmosphere, heated and melted, and polycondensed to obtain a liquid crystal polyester (LCP) having the following theoretical structural formula. -2) was obtained. In addition, the component ratio of a composition represents a molar ratio.

[0050]

[Chemical 9]

The physical properties of each resin composition were evaluated according to the following methods. (1) Molding The obtained pellets are heated to a cylinder temperature of 320/330 /
Injection molding machine [IS-80EPN: Toshiba Machine Co., Ltd.] set to 320/310 ° C, 85% firing speed, and 90 ° C mold temperature.
Molding] was used. (2) Fluidity When the obtained pellet was molded into an ASTM dumbbell test piece having a thickness of 1.6 mm under the molding conditions of (1) above, the gauge pressure was measured when it was shorted by 1 mm.
This pressure is applied to SSP (Short Shot Point).
Was omitted. ) (Kgf / cm ² ), the smaller the value, the better the fluidity. (3) Heat resistance (DTUL) The obtained pellets were molded into an ASTM tanzaku test piece having a thickness of 3.2 mm under the molding conditions of the above (1). The heat distortion temperature under a 1.82 MPa load was measured using the obtained molded piece.

(4) Impact resistance (dirt impact and ductile fracture) The obtained pellets were molded into a flat plate test piece having a thickness of 2.5 mm, a length of 100 mm and a width of 50 mm under the molding conditions of the above (1), and a dart impact. Using a tester (manufactured by Toyo Seiki Co., Ltd.), a drop load of 6.5 kg and a drop height of 100 cm were measured, and the total absorbed energy value, which is the sum of crack energy and propagation energy at the time of breakage, was measured by dirt impact ( J /
m). The larger the value, the better the impact resistance. In addition, when the flat plate test piece after the fracture test is viewed from the thickness direction, the one that is deformed as if the dropped part of the weight is extended is ductile fractured and completely flattened without any deformation. Defined as brittle fracture. Ductile fracture resistance was determined based on the following criteria. Number of tests n
= 5. ◯: All of n = 5 were ductile fractured. (Triangle | delta): Among n = 5, the thing which was ductile fracture 1 to 4 times and the remainder was brittle fracture. X: All of n = 5 were brittle fractured.

[0053]

Examples 1 to 3 PPE produced in Production Example 1 as the component (A) and LC produced in Production Example 2 as the component (B)
As P-1 and (C) component, Tuftec (registered trademark) M1911 (sometimes abbreviated as m-SEBS) manufactured by Asahi Kasei Co., Ltd. and ZnO (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) as (D) component. (Sometimes abbreviated as ZnO) in the proportion (parts by weight) shown in Table 1 is a twin-screw extruder with a vent port (ZSK-25; WERNER &) set at 250 to 300 ° C.
It was melt-kneaded using PFLEIDERER) to obtain pellets. Using these pellets, molding and processing were carried out by the methods shown above, and the physical properties were evaluated. The results are shown in Table 1.

[0054]

[Comparative Examples 1 and 2] PPE produced in Production Example 1 as the component (A) and LC produced in Production Example 2 as the component (B).
Example 1 except that P-1 and m-SEBS as the component (C) were changed to the ratio (parts by weight) shown in Table 1 and the component (D) was omitted.
After carrying out in the same manner as in Example 3 to obtain pellets, molding was carried out by the above-described method and evaluation of physical properties was carried out. The results are shown in Table 1.
It was shown to.

[0055]

Comparative Example 3 P produced in Production Example 1 as the component (A)
PE and LCP produced in Production Example 2 as the component (B)-
As a polymer not functionalized with a functionalized compound as 1 and the component (C), Tuftec (registered trademark) H1041 (may be abbreviated as SEBS) manufactured by Asahi Kasei Corporation
And proportions of ZnO as component (D) shown in Table 1 (parts by weight)
Then, after carrying out in the same manner as in Examples 1 to 3 to obtain pellets,
Molding was performed by the method shown above and physical property evaluation was performed.
The results are shown in Table 1.

[0056]

[Example 4] P produced in Production Example 1 as the component (A)
PE and LCP produced in Production Example 3 as the component (B)-
2 and m-SEBS as the component (C) and ZnO as the component (D) in the proportions (parts by weight) shown in Table 1 were carried out in the same manner as in Examples 1 to 3 to obtain pellets, and then the above was shown. Molding was performed by the method and physical properties were evaluated. The results are shown in Table 1.

[0057]

Comparative Example 4 P produced in Production Example 1 as the component (A)
PE and LCP produced in Production Example 3 as the component (B)-
2 and m-SEBS as the component (C) were carried out in the same manner as in Example 4 except that the ratio (parts by weight) shown in Table 1 was omitted and the component (D) was removed to obtain pellets, followed by the method described above. Molding was carried out and the physical properties were evaluated. The results are shown in Table 1.

[0058]

[Example 5] P produced in Production Example 1 as the component (A)
PE and LCP produced in Production Example 2 as the component (B)-
1 and m-SEBS as the component (C), ZnO as the component (D), and Microglass (registered trademark) RES03-TP30 (sometimes abbreviated as GF) manufactured by Nippon Sheet Glass Co., Ltd. as the component (E) were side-fed. However, the pellets were obtained in the same manner as in Examples 1 to 3 except that the proportions (parts by weight) shown in Table 1 were used. The results are shown in Table 1.

[0059]

[Comparative Example 5] P produced in Production Example 1 as the component (A)
PE and LCP produced in Production Example 2 as the component (B)-
1 and m-SEBS as the component (C) and GF as the component (E) were added while side-feeding so that the proportions (parts by weight) shown in Table 1 were removed and the component (D) was omitted. After carrying out to obtain pellets, molding was carried out by the above-mentioned method and physical properties were evaluated. The results are shown in Table 1.

[0060]

[Example 6] P produced in Production Example 1 as the component (A)
PE and Leona (registered trademark) 1300S (sometimes abbreviated as PA) manufactured by Asahi Kasei Corporation as the component (B), m-SEBS as the component (C) and ZnO as the component (D) are shown in Table 1.
In the same manner as in Examples 1 to 3, the pellets were obtained at the ratio (parts by weight) shown in Table 1, and pellets were obtained. The results are shown in Table 1.

[0061]

Comparative Example 6 P produced in Production Example 1 as the component (A)
PE, PA as the (B) component, and m-S as the (C) component
EBS was carried out in the ratio (parts by weight) shown in Table 1 and the same procedure as in Example 6 was carried out except that the component (D) was omitted. After obtaining pellets, the pellets were molded and processed by the above-described methods to evaluate physical properties. did. The results are shown in Table 1.

[0062]

Example 7 P produced in Production Example 1 as the component (A)
PE and Mitsui PET manufactured by Mitsui Chemicals, Inc. as the component (B),
J125 (sometimes abbreviated as PET), m-SEBS as the (C) component, and ZnO as the (D) component in the proportions (parts by weight) shown in Table 1 were carried out in the same manner as in Examples 1 to 3, and pellets were prepared. After being obtained, molding and processing were carried out by the above-mentioned method, and physical properties were evaluated. The results are shown in Table 1.

[0063]

[Comparative Example 7] P produced in Production Example 1 as the component (A)
PE and PET as the component (B) and m- as the component (C)
SEBS was used in the proportions (parts by weight) shown in Table 1 and the same procedure as in Example 7 was carried out except that the component (D) was omitted. After obtaining pellets, the pellets were molded, and the physical properties were evaluated by the methods described above. did. The results are shown in Table 1.

[0064]

[Table 1]

As shown in Table 1, (A) the polyphenylene ether resin of the present invention, (B) a polymer having a carboxyl group at the terminal, (C) a copolymer of an aromatic vinyl compound and a conjugated diene compound, or A block copolymer of an aromatic vinyl compound and an acrylic vinyl compound, a polymer functionalized with a functionalized compound, and (D) I value,
A resin composition containing a small amount of a compound containing a II- or III-valent metal element can achieve impact resistance, especially dirt impact resistance, molding processability, and heat resistance at a sufficient level at the same time, and particularly the dirt impact characteristics are extremely high. You can see that it can be achieved at a high level.

[0066]

Industrial Applicability According to the present invention, it becomes possible to provide a resin composition which can achieve a high level of impact resistance, particularly dirt impact property, and which has both heat resistance and fluidity.

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Claims (9)

[Claims] 1. (A) Polyphenylene ether-based resin 1
To 99 parts by weight and (B) 100 parts by weight of a resin component consisting of 99 to 1 parts by weight of a polymer having a carboxyl group at the terminal, (C) a block copolymer of an aromatic vinyl compound and a conjugated diene compound, or an aromatic vinyl compound. A block copolymer of a vinyl chloride compound and an acrylic vinyl compound is a compound containing 0.05 to 30 parts by weight of a polymer functionalized with a functionalized compound, and (D) a metal element having a valency of I, II or III. A resin composition comprising 001 to 10 parts by weight. 2. The resin composition according to claim 1, wherein the component (B) is at least one selected from polyamide resins, polyester resins and liquid crystal polyester resins. 3. The resin composition according to claim 1, wherein the component (B) is a liquid crystal polyester resin. 4. The component (C) is a polymer in which a block copolymer of an aromatic vinyl compound and a conjugated diene compound is partially hydrogenated and functionalized with a functionalized compound. The resin composition according to any one of 3 above. 5. The functionalized compound in component (C) is
The resin composition according to any one of claims 1 to 4, which is an α, β-unsaturated carboxylic acid or an α, β-unsaturated carboxylic acid anhydride. 6. The resin composition according to any one of claims 1 to 4, wherein the functionalized compound in the component (C) is maleic acid or maleic anhydride. 7. The resin composition according to claim 1, wherein the component (D) is a zinc compound. 8. The resin composition according to claim 1, wherein the component (D) is zinc oxide. 9. An inorganic filler (E) is further added in an amount of 0.1 to 100 parts by weight with respect to 100 parts by weight of a resin component comprising the components (A) and (B). Item 9. The resin composition according to any one of items 1 to 8.