JPH11106641A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in stability on processing treatments and excellent in thermal stability on practical employment by including polyphenylene ether, an impact resistance-improving material, a specific piperidyl compound and a phosphorous compound in specific amounts, respectively. SOLUTION: This thermoplastic composition comprises (A) 5-99 wt.% of a polyphenylene ether (e.g. 2,6-dimethylphenol polymer), (B) 95-1 wt.% of an impact resistance-improving material (e.g. a styrenic elastomer in which the molecular chain length of a polystyrene segment has a weight-average mol.wt. of >=10,000), (C) at least one of 4-amino-2,2,6,6-tetramethylpiperadyl compounds of formulas I and II in an amount of 0.001-15 pts.wt. per 100 pts.wt. of the components A and B, and (D) at least one kind of phosphorous compound of formula III (R7 -R9 are each phenyl, an alkyl or the like) [e.g. tris(2,4-di-t- butylphenyl)phosphite] similarly in an amount of 0.01-2 pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having improved thermal stability in practical use, in addition to stability during processing in a polyphenylene ether-based resin composition having improved impact resistance. It is about.

[0002]

2. Description of the Related Art Polyphenylene ether resins are thermoplastic resins which are excellent in various properties such as mechanical properties, heat resistance and dimensional stability, but have the drawback of poor fluidity during molding. In addition, when processed at a high temperature, the polyphenylene ether resin is liable to be colored or deteriorated such as cross-linking. Particularly, in the presence of oxygen, deterioration due to heat is remarkable, resulting in gelation and, in some cases, black specs.

In order to compensate for these drawbacks, proposals have been made in terms of processability, such as blending with various resins to lower the temperature during processing. Further, in order to suppress thermal deterioration, it has been proposed to blend various additives. For example, a phosphorus-based additive as disclosed in JP-B-44-29751 and a phenol-based additive as disclosed in JP-B-46-24782 can be exemplified. JP-A-52-141883 and JP-A-58-194931.
JP-A-60-76538, JP-A-60-76538
149646, JP-A-60-168755, JP-A-60-168756, JP-A-60-1
No. 99035, JP-A-60-203150,
JP-A-60-221452, JP-A-61-203
No. 150, JP-A-62-192454, JP-A-62-283183, JP-A-1-126364
And various compounds containing sterically hindered amines, mainly for the purpose of preventing discoloration due to light, and compounds containing sterically hindered amines and phenol-based additives, as shown in JP-A-1-161051. Numerous studies have been made, such as using together. Recently, Japanese Patent Application No. 8-34983 has found that a specific hindered amine compound can stabilize a polyphenylene ether-based resin. However, when a polyphenylene ether-based resin is usually used, an impact resistance improving material is added to improve the impact strength, but after stabilizing the polyphenylene ether, the newly added impact resistance improving material is added. Sufficient stabilization has not been attained, and for example, problems such as the bleeding of the surface of the molded article while the decomposition product of the impact resistance improving material has been used for a long time have occurred. As for the stabilization of the impact modifier at the time of high-temperature processing, a stabilizer of a hindered phenol compound, a sulfur compound or a phosphorus compound was examined, and bis (2,6-t-butyl-4-methylphenyl) pentane was examined. Erythritol diphosphite was most effective, but when coexisted with the compound described in Japanese Patent Application No. 8-34983, which is effective for stabilizing polyphenylene ether, the stabilizing effect of polyphenylene ether was inhibited. As described above, stabilization of polyphenylene ether and stabilization of the impact resistance improving material have not yet been achieved at the same time.

[0004]

Under such circumstances, the problem to be solved by the present invention is to achieve a sufficient stabilization of the polyphenylene ether in the polyphenylene ether-based resin and to further improve the impact by improving the impact. Another object of the present invention is to provide a composition in which the impact modifier is stabilized.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above problems, and as a result, have found that a specific hindered piperidine-based compound and a specific phosphorus-based compound can be added to a composition of polyphenylene ether and an impact modifier. The present inventors have found that the addition of the compound has an effect of remarkably improving the heat stability of the polyphenylene ether and the impact modifier due to heat during processing, and have completed the present invention.

That is, the present invention provides the following (A) to (D)
Wherein the content of (A) is from 5 to 99% by weight and the content of (B) is from 95 to 1% by weight (where,
The total amount of (A) and (B) is 100% by weight. ),
The content of (C) is 0.001 to 15 parts by weight per 100 parts by weight of the total amount of (A) and (B), and the content of (D) is 100% by weight of the total amount of (A) and (B). The present invention relates to a thermoplastic resin composition which is 0.01 to 2 parts by weight per part by weight. (A): polyphenylene ether (B): impact modifier (C): at least one 4-amino-2,2,6,6-tetramethylpiperidyl represented by the following general formula (1) or (2) Compound (D): at least one phosphorus compound represented by the following general formula (6)

[In the formulas (1) and (2), R ₁ represents a hydrogen atom, an oxygen atom (oxy radical), a hydroxyl group, an alkyl group, a cycloalkyl group, an allyl group, a benzyl group, an aryl group, an alkanoyl group, an alkenoyl group. R ₂ represents a hydrogen atom, an alkyl group, or the above formula (3), and R ₃ represents n
Represents a valence group, n represents an integer of 1 to 4, and q represents an integer of 2 to 6. [In the formula (3), R ₄ represents a direct bond, a linear or branched alkylene group, or an alkylidene group or an arylene group, and R ₅ represents a hydrogen atom, an alkyl group, an aryl group, the general formula (4) or ( X represents a direct bond, -O-
Or -NH-. [In the formula (5), R ₆ represents a hydrogen atom, an oxygen atom (oxy radical), a hydroxyl group, an alkyl group, a cycloalkyl group, an allyl group, a benzyl group, an aryl group, an alkanoyl group, an alkenoyl group, an alkyloxy group or a cyclooxy group. Represents an alkyloxy group. In the formula (6), R ₇ —O—, R ₈ —O— and R ₉ —
Both O- rather those derived by pentaerythritol, R _7, R ₈ and R ₉ represents a phenyl group, an alkyl group, and derivatives thereof. ]

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polyphenylene ether as the component (A) of the present invention is obtained by oxidizing one or more phenolic compounds represented by the following general formula with oxygen or an oxygen-containing gas using an oxidative coupling catalyst. It is a polymer obtained by polymerization. [Wherein, R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are selected from hydrogen, a halogen atom, a hydrocarbon group or a substituted hydrocarbon group, and one of them is always a hydrogen atom . ]

In the above general formula, R ₁₂ , R ₁₃ , R ₁₄ , R
Specific examples of ₁₅ and R ₁₆ include hydrogen, chlorine, bromine, fluorine, iodine, methyl, ethyl, n- or iso-propyl, pri-, sec- or t-butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl , Hydroxymethyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl,
Methylphenyl, dimethylphenyl, ethylphenyl,
Allyl and the like.

Specific examples of the above general formula include phenol, o-, m-, or p-cresol, 2,6-, 2,
5-, 2,4- or 3,5-dimethylphenol, 2-
Methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-diethylphenol, 2-methyl-6-ethylphenol, 2,3,5-, 2,3,6-
Or 2,4,6-trimethylphenol, 3-methyl-
6-t-butylphenol, thymol, 2-methyl-6
-Allylphenol and the like.

The phenol compound of the above general formula is a phenol compound other than the above general formula, for example, bisphenol-A, tetrabromobisphenol-A, resorcinol,
It can also be copolymerized with a polyvalent hydroxy aromatic compound such as hydroquinone or novolak resin.

Preferred as the polyphenylene ether of the component (A) are a homopolymer of 2,6-dimethylphenol or 2,6-diphenylphenol, a large part of 2,6-dimethylphenol and a small part of 3- Copolymers of methyl-6-t-butylphenol or 2,3,6-trimethylphenol are exemplified.

The oxidative coupling catalyst used in the oxidative polymerization of the phenol compound is not particularly limited, and any catalyst having a polymerization ability can be used.

A styrene elastomer is used as the impact modifier which is the component (B) of the present invention. Here, known styrene elastomers can be used. For example, a styrene-butadiene block copolymer having one or more polystyrene and polybutadiene segments, a styrene-isoprene copolymer having one or more polystyrene and polyisoprene segments, and one or more copolymers of polystyrene and isoprene-butadiene are provided. Having a block copolymer,
Alternatively, styrene is graft-polymerized on a polyolefin elastomer obtained by copolymerizing ethylene, propylene, butene, and a diene component with a block copolymer in which the unsaturated portion of the isoprene portion or the butadiene portion is selectively hydrogenated.

The molecular chain length of the polystyrene segments in these styrene elastomers is preferably 10,000 or more in terms of weight average molecular weight. If the polystyrene segment is too short, the compatibility with the PPE-based resin composition will be reduced, and delamination will occur during injection molding, or sufficient impact resistance will not be obtained, which is not preferable. In particular, from the viewpoint of stability at the time of processing at a high temperature, a preferable impact modifier is a styrene block copolymer in which an unsaturated portion of an isoprene portion or a butadiene portion is selectively hydrogenated, and ethylene, propylene, It is obtained by graft-polymerizing styrene onto a polyolefin elastomer obtained by copolymerizing butene and diene components.

The component (C) of the present invention is at least one 4-amino-2,2,6,6-tetramethylpiperidyl compound represented by the following general formula (1) or (2).

In the general formulas (1) and (2), R
₁ is a hydrogen atom, an oxygen atom (oxy radical), a hydroxyl group,
R represents an alkyl group, a cycloalkyl group, an allyl group, a benzyl group, an aryl group, an alkanoyl group, an alkenoyl group, an alkyloxy group or a cycloalkyloxy group;
₂ represents a hydrogen atom, an alkyl group, or the above general formula (3);
R ₃ represents an n-valent group, n represents an integer of 1 to 4, and q represents an integer of 2 to 6.

In the general formula (3), R ₄ represents a direct bond, a linear or branched alkylene group, or an alkylidene group or an arylene group, and R ₅ represents a hydrogen atom, an alkyl group, an aryl group, or a compound represented by the general formula (4) ) Or (5),
X represents a direct bond, -O- or -NH-.

In the general formula (5), R ₆ is a hydrogen atom, an oxygen atom (oxy radical), a hydroxyl group, an alkyl group, a cycloalkyl group, an allyl group, a benzyl group, an aryl group, an alkanoyl group, an alkenoyl group, an alkyloxy group. A cycloalkyloxy group or a cycloalkyloxy group.

Preferred examples of the component (C) include at least one component represented by the general formula (2) or (3).
-Amino-2,2,6,6-tetramethylpiperidyl compound wherein n = 1 and R ₃ is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a benzyl group, an aryl group or the following general formula (7) Can be given. [In the formula (7), Y is a direct bond, —O— or NR ₁₂
R ₁₀ is a direct bond, a linear or branched alkylene group, or an alkylidene group, an arylene group,
R ₁₁ and R ₁₂ independently represent a hydrogen atom, a hydroxyl group, an alkyl group, or an aryl group. ]

More preferably, when n = 1, R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, Represented by an alkenyl group, a benzyl group, an aryl group or the formula (7), wherein Y is a direct bond, -O
- or NR ₈ - is represented by, R ₆ is a direct bond, a linear or branched alkylene group having 1 to 10 carbon atoms, or alkylidene group, is represented by an arylene group, hydrogen R _7, R ₈ are independently of each other An atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 21 carbon atoms, and a compound represented by the formula (4) or (5). Another preferred example is that, when n = 2, in the general formula (1), R ₃ is an alkylene group or a formula (7) A compound representing R ₉ represents a direct bond, a linear or branched alkylene group, an alkylidene group having 1 to 10 carbon atoms, or an arylene group. Alternatively, it is represented by equation (4).

More preferably, when n = 2, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and R ₃ represents an alkylene group or a compound of the formula (7) Wherein R ₉ represents a direct bond, a linear or branched alkylene group having 1 to 10 carbon atoms, an alkylidene group having 1 to 10 carbon atoms, or an arylene group. When n = 2, in the general formula (1), R ₂ is represented by the formula (3) Where X is a direct bond, -O- or -NH-
Wherein R ₄ is a direct bond, a linear or branched alkylene group, or an alkylidene group or an arylene group;
₅ is a hydrogen atom, an alkyl group, an aryl group, a compound represented by the formula (4) or the formula (5), and a compound in which R ₃ is an alkylene group is also preferable. Specifically, Japanese Patent Application No. 8-34983
The compounds described above can be mentioned.

The component (D) of the present invention has the general formula (6)
And at least one phosphorus compound represented by

In the general formula (6), R ₇ —O—,
Neither R ₈ —O— nor R ₉ —O— was derived from pentaerythritol, and R ₇ , R ₈ and R ₉ represent phenyl, alkyl and derivatives thereof.

In the general formula (6), preferably, R
_10, at least two phenyl groups among of R _11, R _12, including substituted phenyl group, also even these R _10, R _11, R ₁₂ independently may be bonded to each other. R ₁₀ , R
_At least two of ₁₁ and R ₁₂ are a phenyl group or a substituted phenyl group. A substituted phenyl group is a substituted phenyl group in which one or more hydrogen has been replaced by an alkyl group. Examples of the alkyl group to be substituted include a methyl group, an ethyl group,
Examples include a propyl group and a t-butyl group. Particularly, a substituted phenyl group substituted by one or more t-butyl groups is preferred. These adjacent substituted phenyl groups may be covalently linked to each other.

As a specific compound, tris (2,4
-Di-t-butylphenyl) phosphite, tris (mono, dinonylphenyl) phosphite and triphenylphosphite. ,

The thermoplastic resin composition of the present invention contains the above components (A) to (D), and the content of (A) is 5 to 5.
99% by weight, and the content of (B) is 95 to 1% by weight (where the total amount of (A) and (B) is 100% by weight).
And ), The content of (C) is 0.001 to 15 parts by weight per 100 parts by weight of the total amount of (A) and (B);
And the content of (D) is 100 in total of (A) and (B).
It is a thermoplastic resin composition in an amount of 0.01 to 2 parts by weight per part by weight. If the content of (A) is too large, the impact resistance becomes poor, while if the content of (B) is too large, the heat resistance becomes poor.
If the amount of (C) is too small, the deterioration of the polyphenylene ether cannot be suppressed, while if the amount of (C) is too large, the transpiration component increases and the mechanical properties decrease. If the content of (D) is too small, the stabilization of the impact resistance improving material is insufficient, while if the content of (D) is too large, the amount of transpiration components is increased, and mold contamination and the like during injection molding become remarkable.

The thermoplastic resin composition of the present invention contains (E) an alkenyl aromatic copolymer in addition to the above (A) to (D), and the content of (A) is 5 to 98% by weight. , Preferably 5 to 90% by weight, and the content of (B) is 1 to 95% by weight.
%, Preferably 5 to 50% by weight, and the content of (E) is 1 to 94% by weight, preferably 5 to 90% by weight, wherein (A), (B) and (E) ) Total amount 10
0% by weight. ) And (C) are 0.001 to 15 parts by weight per 100 parts by weight of the total amount of (A) and (B), and the content of (D) is the total of (A) and (B). The thermoplastic resin composition can be 0.01 to 2 parts by weight per 100 parts by weight. By using (E) within this range, the effect of improving fluidity can be obtained.

The alkenyl aromatic copolymer of the component (E) is generally known to those skilled in the art, and is a homopolymer or a copolymer having a repeating unit of the following general formula derived from an aromatic vinyl compound. It is. [Where R represents hydrogen, alkyl having 1 to 6 carbons or halogen, Y represents hydrogen, vinyl, halogen, an amino group or alkyl having 1 to 6 carbons, and 1 is an integer of 0 or 1 to 5; Represents ]

The alkenyl aromatic resin is, for example, a polymer comprising one or more polymer units selected from styrene, α-methylstyrene, p-methylstyrene and the like, and polystyrene (PS) ), Polychlorostyrene, polyα-methylstyrene, styrene-acrylonitrile copolymer (AS resin), styrene-α-methylstyrene copolymer, styrene-4-methylstyrene copolymer, styrene-maleic anhydride copolymer Coalescence, styrene-
Methyl methacrylate copolymer (MS resin) is mentioned.

Further, a copolymer of a compound containing two or more vinyl groups such as divinylbenzene and ethylene glycol dimethacrylate with the above-mentioned aromatic vinyl compound is also included.

Most of these alkenyl aromatic resins generally have an atactic structure, but the alkenyl aromatic resin used in the present invention may have a syndiotactic structure. An alkenyl aromatic resin having a syndiotactic structure is mainly composed of a syndiotactic structure having a stereochemical structure,
A phenyl group or substituted phenyl group, which is a side chain with respect to the main chain formed from carbon bonds, has a three-dimensional structure in which the phenyl group and the substituted phenyl group are alternately located in the opposite direction. ( ^13C -NMR method). Tacticity measured by the ¹³ C-NMR method can be represented by the proportion of a plurality of continuous constituent units, for example, a dyad in the case of two, a triad in the case of three, and a pentad in the case of five. However, the styrenic polymer having a syndiotactic structure referred to in the present invention usually has a syndiotacticity of 85% or more in dyad or 35% or more in pentad (racemic pentad), preferably 50% or more. Polystyrene, poly (alkylstyrene), poly (halogenated styrene), poly (alkoxystyrene), poly (benzoic acid ester styrene), a mixture thereof, or a copolymer containing these as a main component. The poly (alkyl styrene) includes poly (methyl styrene), poly (ethyl styrene), poly (isopropyl styrene), poly (tertiary butyl styrene) and the like, and poly (halogenated styrene) includes Examples include poly (chlorostyrene) and poly (bromostyrene). Examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene). In the present invention,
Two or more of those having a syndiotactic structure and those having an atactic structure may be used in combination.

The alkenyl aromatic resins also include those modified with rubber. That is, a rubbery polymer is dispersed in an alkenyl aromatic resin matrix. The rubbery polymer used here is a rubbery polymer and copolymer containing a diene component, specifically, polybutadiene, polyisoprene, polychlorobutadiene, butadiene-styrene copolymer, isoprene-styrene copolymer, Examples thereof include a butadiene-acrylonitrile copolymer, a copolymer of isobutylene and butadiene or isoprene, an ethylene-propylene copolymer, and an ethylene-propylene-nonconjugated diene copolymer. Various methods are known for dispersing this rubbery polymer in a styrene resin,
For example, any method such as a method of mechanical mixing, a solution blending method, and a method of dissolving a rubbery polymer in a styrene monomer and graft-copolymerizing the styrene monomer may be used. The polymerization method includes emulsion polymerization and bulk polymerization (Japanese Patent Publication No. Sho 4
2-662, US Pat. No. 3,435,096), a solution polymerization method (US Pat. No. 3,538,190, US Pat.
No. 8191) and suspension polymerization (JP-B-49-1083).
No. 1, JP-B-57-40166, JP-B-62
-10565)). The ratio of the rubber-like polymer of the rubber-modified styrene-based resin and the styrene-based resin is 0.5 to
It is 80% by weight, preferably 0.5 to 50% by weight.

Specifically, high impact polystyrene (HIP
Butadiene rubber-modified polystyrene, styrene-butadiene rubber-modified polystyrene, ethylene-propylene-non-conjugated diene rubber-modified polystyrene, etc., which are commercially available as S), acrylonitrile-butadiene-styrene copolymer known as ABS resin, and AES Acrylonitrile- (ethylene-
Propylene- (non-conjugated diene) rubber.

In the present invention, a filler can be compounded for the purpose of improving the rigidity and the hardness of the polyamide-polyphenylene ether resin. As a suitable filler,
Calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, zinc oxide, titanium oxide, magnesium oxide, magnesium sulfate, aluminum silicate, magnesium silicate, calcium silicate, silicic acid,
Inorganic fibers such as hydrous calcium silicate, hydrous aluminum silicate, mica, mineral fiber, zonotolite, potassium titanate whisker, magnesium oxysulfate, glass balun, glass fiber, glass beads, carbon fiber, stainless steel fiber, aramid fiber, carbon black However, one or more of these fillers can be blended. The filler to be blended is not limited to these.

In the present invention, in order to obtain a thermoplastic resin composition, a filler can be blended and used for the purpose of strengthening, imparting functions, and the like.

Examples of the filler include glass fibers, carbon fibers, aramid fibers, reinforcing fibers such as aluminum and stainless steel, and metal whiskers, silica, alumina, calcium carbonate, talc, mica, clay, kaolin, and sulfuric acid. Magnesium, carbon black, TiO ₂ , ZnO
And it is possible to use an inorganic filler such as Sb ₂ O _3.

Further, in the present invention, for example, Japanese Patent Application No. Hei 9-3
It is also effective to stabilize the alkenyl aromatic polymer with a hindered phenol compound and a sulfur compound as described in JP-A-7496. Specifically, they are the following compounds. [In the formula (9), X represents the formula (10). [In the formula (10), R ₁₈ represents an alkyl group having 1 to 3 carbon atoms. [In the formula (11), R ₁₉ represents an alkyl group having 4 to 20 carbon atoms. [In the formula (12), R ₂₀ represents an alkyl group having 3 to 18 carbon atoms. [In the formula (13), R ₂₁ represents an alkyl group having 12 to 14 carbon atoms. ]

The thermoplastic resin composition of the present invention can be obtained by the following a)
To e) are obtained by blending the components by a known method and melt-kneading. Also, it may be added in the polymerization step of component a).

The thermoplastic resin composition of the present invention can be obtained by injection molding,
A wide range of moldings, such as blow molding, sheet molding, film molding, and vacuum molding, are possible. Particularly, blow molding, sheet molding, and film molding are optimal because deterioration due to heat is significantly suppressed. Further, the obtained molded article can be widely used as a packaging material, a home appliance, an outer panel component for an automobile, and an interior material.

[0041]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

The following compounds were used in the examples. PPE-A : polyphenylene ether resin, YPX1
00F poly (2,6-dimethyl-1,4-phenylene) ether, manufactured by Mitsubishi Gas Chemical Co., Ltd., PPE-B corresponding to the component (A) of the present invention: polyphenylene ether resin, intrinsic viscosity (chloroform, (25 ° C.) 0.46 dl / g poly (2,6-dimethyl-1,4-phenylene) ether, manufactured by Nippon Polyether Co., Ltd., PS corresponding to the component (A) of the present invention: PS : polystyrene, Sumibright E183K (Trademark: manufactured by Sumitomo Chemical Co., Ltd.), SEBE corresponding to the component (B) of the present invention: hydrogenated styrene-butadiene copolymer, Septon 8006 (trademark: manufactured by Kuraray Co., Ltd.), component of the present invention ( Additive C-1): N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) 1,6-hexanediamine Additive-2 : Sumilizer-GA80 (trademark: Sumitomo) Chemistry Industrial Co., Ltd.), 3,9-bis (2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy) -1,1-dimethylethyl) -2,4 ,
8,10-tetraoxaspio (5,5) undecane,
Additive-3 , a compound belonging to the general formula (1) of the present invention: Sumilizer-TPD (trademark: manufactured by Sumitomo Chemical Co., Ltd.), pentaerythrityl-tetrakis (3-laurylthiopropionate), Additive-4 which is a compound belonging to the general formula (2) of the invention: Tris (2,4-di-t-butylphenyl) phosphite Additive-5 : Bis (2,6-t-butyl-4-methyl) Phenyl) pentaerythritol diphosphite Additive-6 : Pigment : carbon black # 750B, manufactured by Mitsubishi Chemical

Example 1 and Comparative Example 1 After blending each component at the ratio (weight ratio) shown in Tables 1 and 2, TEM-50A (Toshiba Machine 50 mm twin screw extruder) and IS220EN (Toshiba Machine Mold) Tightening force 220
The mixture was melt-kneaded under the conditions shown in Table 1, pelletized, and injection-molded to obtain a molded product. The obtained pellets were injection molded at 310 ° C. to form test pieces, and various evaluations were made. Table 2 shows the evaluation results. The evaluation was performed as follows. (1) Izod impact strength: Measured with a notch on a 3.2 mm thick test piece according to ASTM D256. (2) Flexural modulus: Measured according to ASTM D790. (3) Heat distortion temperature (HDT): ASTM Measured under a load of 18.6 kg according to D648. (4) Smoothness of flat plate: visually evaluated

[0044]

[Table 1]

[0045]

[Table 2]

In Examples 2 and 3, and Comparative Example 2, the stabilizing effect of polyphenylene ether was set to the formula shown in Table 3 by using a laboplast mill (manufactured by Toyo Seiki Co., Ltd.) at 300 ° C. in order to easily confirm the effect. And kneading at 90 rpm for 30 minutes. The results are shown in Table 3 showing the presence or absence of gelation, the final torque, and the molecular weight of the polyphenylene ether after kneading.

(Molecular weight of polyphenylene ether) The obtained pellet was dissolved in chloroform and subjected to gel permeation chromatography (GPC) (HLC-80 manufactured by Tosoh Corporation).
20 columns: K-806, K-805, K-804,
K-803 Detector: UV 290 nm Temperature: 40 ° C
(Flow rate: 1.0 ml / min), and the molecular weight in terms of polystyrene was determined.

[0048]

[Table 3]

[0049]

By adding a specific hindered piperidine compound and a specific phosphorus compound to the composition of the polyphenylene ether and the impact modifier, the polyphenylene ether and the impact modifier due to heat during processing can be obtained. The heat stability is significantly improved.

Claims (6)

[Claims] 1. It contains the following components (A) to (D),
The content of (A) is 5 to 99% by weight, and the content of (B) is 95 to 1% by weight (where (A) and (B)
Of 100% by weight. ) And (C) are 0.000 parts by weight per 100 parts by weight of the total of (A) and (B).
A thermoplastic resin composition comprising 1 to 15 parts by weight, and wherein the content of (D) is 0.01 to 2 parts by weight per 100 parts by weight of the total of (A) and (B). (A): polyphenylene ether (B): impact modifier (C): at least one 4-amino-2,2,6,6-tetramethylpiperidyl represented by the following general formula (1) or (2) Compound (D): at least one phosphorus compound represented by the following general formula (6) [In the formulas (1) and (2), R ₁ represents a hydrogen atom, an oxygen atom (oxy radical), a hydroxyl group, an alkyl group, a cycloalkyl group, an allyl group, a benzyl group, an aryl group, an alkanoyl group, an alkenoyl group, an alkyl Represents an oxy group or a cycloalkyloxy group, R ₂ represents a hydrogen atom, an alkyl group, or the above general formula (3); R ₃ represents an n-valent group; n represents an integer of 1 to 4; Represents an integer of 2 to 6. [In the formula (3), R ₄ represents a direct bond, a linear or branched alkylene group, or an alkylidene group or an arylene group, and R ₅ represents a hydrogen atom, an alkyl group, an aryl group, the general formula (4) or ( X represents a direct bond, -O-
Or -NH-. [In the formula (5), R ₆ represents a hydrogen atom, an oxygen atom (oxy radical), a hydroxyl group, an alkyl group, a cycloalkyl group, an allyl group, a benzyl group, an aryl group, an alkanoyl group, an alkenoyl group, an alkyloxy group or a cyclooxy group. Represents an alkyloxy group. In the formula (6), R ₇ —O—, R ₈ —O— and R ₉ —
Both O- rather those derived by pentaerythritol, R _7, R ₈ and R ₉ represents a phenyl group, an alkyl group, and derivatives thereof. ] 2. The impact modifier of component (B) is a styrene-based block copolymer in which unsaturated portions of isoprene and butadiene are selectively hydrogenated, or ethylene, propylene, butene, and diene components. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is at least one polymer selected from a copolymer of polystyrene and styrene graft-polymerized. 3. At least one 4-amino-2,2,6,6 represented by the general formula (2) or (3) of the component (C)
A tetramethylpiperidyl compound wherein n = 1 and R ₃ is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a benzyl group, an aryl group or the following general formula (7)
The thermoplastic resin composition according to claim 1, represented by the following formula: [In the formula (7), Y is a direct bond, —O— or NR ₁₂
R ₁₀ is a direct bond, a linear or branched alkylene group, or an alkylidene group, an arylene group,
R ₁₁ and R ₁₂ independently represent a hydrogen atom, a hydroxyl group, an alkyl group, or an aryl group. ] 4. The at least one phosphorus compound represented by the general formula (6) of the component (D), wherein at least two of R ₇ , R ₈ and R ₉ are a phenyl group or a substituted phenyl group. 2. The thermoplastic resin composition shown in 1. 5. The alkenyl aromatic copolymer of (A) to (D) and (E) according to claim 1, wherein the content of (A) is 5 to 98% by weight, Content is 1-9
5% by weight, the content of (E) is 1 to 94% by weight, (here, the total amount of (A), (B) and (E) is 10%).
0% by weight. ) And (C) are 0.001 to 15 parts by weight per 100 parts by weight of the total amount of (A) and (B), and the content of (D) is the total of (A) and (B). The thermoplastic resin composition according to any one of claims 1 to 4, wherein the amount is 0.01 to 2 parts by weight per 100 parts by weight. 6. The content of (A) is 5 to 90% by weight, the content of (B) is 5 to 50% by weight, the content of (E) is 5 to 90% by weight, (Where (A),
The total amount of (B) and (E) is 100% by weight. ),
The content of (C) is 0.001 to 15 parts by weight per 100 parts by weight of the total amount of (A) and (B), and the content of (D) is 100% by weight of the total amount of (A) and (B). The thermoplastic resin composition according to claim 5, wherein the amount is 0.01 to 2 parts by weight per part by weight.