JP2001323154A - Flame retardant polyether resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyphenylene ether resin composition excellent in flame retardance and mechanical characteristics free from a halogen compound or a phosphorus compound, and is environmentally preferable. SOLUTION: A flame retardant polyether resin composition comprises: a polyphenylene ether resin using a part or all of a functionalized compound manufactured by reacting a mixture added with a functionalized compound having at least one carbon-carbon double bond or a triple bond and at least one of at least one carboxylic acid group, an oxidized acyl group and an imide group in the molecular structure at a reaction temperature from a room temperature or more to the melting point or below of the polyphenylene ether; an organopolysoloxane containing a modified organopolysiloxane having at least one of an amino group, an imide group and an epoxy group in the molecule to a styrene resin; and a cyclic nitrogen compound used if necessary.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an environmentally preferable flame-retardant resin composition.

[0002]

2. Description of the Related Art Flame-retardant synthetic resins have generally been made flame-retardant by, for example, adding halogen compounds, phosphorus compounds, and their combination, or adding antimony trioxide. Has been used. However, these conventional flame retardants are said to be harmful, and recently there has been a demand for a flame retardant resin composition containing no halogen, antimony, phosphorus or the like, particularly from an environmental point of view.

As a flame-retardant resin composition preferable for the environment, a material containing a large amount of a metal hydroxide has been developed. However, not only the specific gravity of the material is greatly increased, but also the impact resistance and the molding property are improved. At present, the fluidity is large and the practicality is poor.

On the other hand, Japanese Patent No. 1684119, Japanese Patent No. 1935582, Japanese Patent Application Laid-Open No. 10-139964, Japanese Patent Application Laid-Open No. 11-140294, Japanese Patent Application Laid-Open No.
JP-A-222559 discloses a flame-retardant resin composition by blending a specific silicone compound. Further, even if a silicone compound is added, it is difficult to obtain flame retardancy. Therefore, Japanese Patent Nos. 2,719,486, 2,746,519 and 11-217494 disclose a silicone compound and a perfluoroalkanesulfonic acid. A polycarbonate resin-based flame retardant resin composition using a metal salt in combination is disclosed. However,
The perfluoroalkanesulfonic acid metal salt contains fluorine and cannot be said to be a flame-retardant resin composition using no halogen, and has almost no flame-retardant effect except for polycarbonate resin.

As typical flame-retardant resins which do not contain halogen-based flame retardants other than polycarbonate resins, polyphenylene ethers to which phosphorus-based flame retardants have been added and polymer blends thereof with polystyrene have been known. A flame retardant resin composition containing a silicone compound in a polyphenylene ether-based resin is disclosed in Japanese Patent No. 1935582, and a flame retardant resin composition using a modified silicone is disclosed in JP-A-2000-109680. I couldn't do it.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a flame-retardant resin composition which does not contain a halogen compound or a phosphorus compound and is environmentally preferable and has excellent mechanical properties.

[0007]

Means for Solving the Problems As a result of diligent studies on the technology for achieving the above-mentioned object, the present inventors have found that a new technique has been proposed in which modified organopolysiloxane is mixed with modified polyphenylene ether obtained by a new method. The inventors have found that a flame-retardant resin composition having excellent mechanical properties can be obtained by the flame-retarding technique, and have completed the present invention.

That is, according to the present invention, at least one carbon-carbon double bond or triple bond, and at least one carbon-carbon double bond or A mixture containing 0.01 to 10.0 parts by weight of a functionalized compound (b) having at least one of a carboxyl group, an acyl oxide group, and an imide group is added at room temperature or higher to the polyphenylene ether (a-1). Functionalized polyphenylene ethers prepared by reacting at a reaction temperature below the melting point (a-2)
A modified organopolysiloxane having at least one of an amino group, an imide group and an epoxy group in the molecule, based on 100 parts by weight of the total of the polyphenylene ether resin (A) and the styrene resin (B) in which a part or all of the above are used. Organopolysiloxane containing siloxane (C) 0.1 to 15
The present invention provides a flame-retarded polyether resin composition containing 1 part by weight and 0 to 15 parts by weight of a cyclic nitrogen compound (D).

[0009]

Embedded image

[R ₁ and R ₄ are each independently hydrogen, halogen, primary or secondary lower alkyl,
Represents phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy (provided that at least two carbon atoms separate a halogen atom and an oxygen atom), and R ₂ and R ₃ are each independently , Hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy, or halohydrocarbonoxy, provided that at least two carbon atoms separate the halogen and oxygen atoms. Express. ]

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS (a-1) and (a-2) used as the polyphenylene ether resin (A) of the present invention
Is described below. The reduced viscosity of the polyphenylene ether (a-1) of the present invention measured at 30 ° C. using a chloroform solution of 0.5 g / dl is 0.15 to 1.
0 dl / g, more preferably 0.20 to 0.70
Polymer or copolymer in the range of dl / g.

The polyphenylene ether of the present invention (a-
1) is a polyphenylene ether having a main chain structure of the formula (1),

Embedded image

[R ₁ and R ₄ are each independently hydrogen,
Halogen, primary or secondary lower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy, provided that at least two carbon atoms separate the halogen atom from the oxygen atom Express. R ₂ and R ₃ are each independently hydrogen, halogen, primary or secondary lower alkyl, phenyl,
Represents haloalkyl, hydrocarbonoxy, or halohydrocarbonoxy, provided that at least two carbon atoms separate a halogen atom and an oxygen atom. Specifically, poly (2,6-dimethyl-1,4-phenylene ether), 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).

The polyphenylene ether (a-
1) Another specific example is polyphenylene such as a copolymer of 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol or 2-methyl-6-butylphenol). An ether copolymer is also included. Among the above-mentioned polyphenylene ethers (a-1) of the present invention, poly (2,6-dimethyl-1,4-
(Phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol can be preferably used, and most preferred is poly (2,6-dimethyl-1,4-phenylene ether). .

As an example of the method for producing the polyphenylene ether (a-1) used in the present invention, US Pat.
874, there is a method in which 2,6-xylenol is oxidatively polymerized using a complex of a cuprous salt and an amine as a catalyst. U.S. Pat. No. 3,306,875;
257357 and 3257358,
JP-B-52-17880 and JP-A-50-5119
Nos. 7 and 63-152628 are also preferable as a method for producing polyphenylene ether (a-1).

The polyphenylene ether of the present invention (a-
The terminal structure of 1) is preferably a structure of the following (formula 2).

Embedded image [Wherein, R ₁ , R ₂ , R ₃ , and R ₄ are each the same as in the above formula (1)
Is defined similarly to R ₁ , R ₂ , R ₃ , and R ₄ . ]

The polyphenylene ether of the present invention (a-
More preferably, the terminal structure of 1) has a structure of the following (formula 3).

Embedded image Wherein R ₅ and R ₅ ′ represent an alkyl group. ]

The modifier (b) used in the present invention is a modifier selected from a conjugated non-aromatic diene compound, a dienophile compound having one dienophile group, or a precursor of these dienes or dienophile compounds. . Among these modifiers (b), at least one carbon-carbon double bond or triple bond and at least one carboxyl group, acyl oxide group, imino group, imido group, hydroxyl group,
It is preferable that the compound has at least one glycidyl group in its molecular structure.

The modifier (b) of the present invention is most preferably maleic anhydride, maleic acid, fumaric acid, phenylmaleimide, itaconic acid, glycidyl methacrylate, or glycidyl acrylate. In the process for producing the functionalized polyphenylene ether (a-2) according to the present invention, the polyphenylene ether (a-1) 100
0.01 to 10.0 parts by weight of the above modifier (b) is mixed with and reacted with parts by weight.

When the modifier (b) is less than 0.01 parts by weight, the amount of the functional group is insufficient. 10. Modifier (b) is 10.
If the amount exceeds 0 parts by weight, a large amount of the unreacted modifier (b) remains in the functionalized polyphenylene ether resin,
It causes silver streaks when molding. In the present invention, polyphenylene ether (a-1) 100
0.1 to 5.0 parts by weight of the modifier (b) based on parts by weight
Are preferably mixed and reacted.

Further, polyphenylene ether (a-
1) More preferably, 0.5 to 3.0 parts by weight of the modifier (b) is mixed with 100 parts by weight and reacted. Functionalized polyphenylene ether of the present invention (a-2)
, The reaction temperature is not lower than room temperature and not higher than the melting point of the polyphenylene ether (a-1). In the present invention, room temperature is 27 ° C.

In the present invention, when the reaction temperature is lower than room temperature, the polyphenylene ether (a-1) and the modifier (b)
Does not react well. In the present invention, crystalline polyphenylene ether having a melting point is used as the raw material polyphenylene ether (a-1). Documents showing the relationship between crystalline polyphenylene ether and its melting point include, for example,
Journal of Polymer Science
e, Part A-2 (6) 1141-1148 (1
968), European Polymer Jo
urnal (9) p. 293-300 (1973), P.
polymer (19), pp. 81-84 (1978).

In the present invention, the polyphenylene ether (a
The melting point of -1) is the peak of the peak observed in the temperature-heat flow graph obtained when the temperature is increased at 20 ° C./min in the measurement of the differential thermal scanning calorimeter (DSC) for (a-1). Defined by top temperature. In the present invention, the melting point of polyphenylene ether (a-1) is defined by the highest temperature among a plurality of peak top temperatures when there are a plurality of them.

In the process for producing a functionalized polyphenylene ether resin of the present invention, the polyphenylene ether (a
-1) is a powdery substance obtained by precipitation from a solution, and is preferably a polyphenylene ether having a melting point of 240 ° C to 260 ° C. In the method for producing a functionalized polyphenylene ether (a-2) of the present invention, the polyphenylene ether (a-1) is a powdery substance obtained by precipitation from a solution, and has a heat of fusion obtained from a peak in a DSC measurement. (ΔH) is preferably 2 J / g or more.

In the present invention, when the reaction temperature exceeds the melting point of the polyphenylene ether (a-1), the polyphenylene ether (a-1) melts and the viscosity increases, so that mixing with the modifier (b) is hindered. And does not accelerate the reaction. At this time, when the polyphenylene ether (a-1) and the modifier (b) are strongly kneaded to promote the reaction, the color tone and appearance of the polyphenylene ether (a-1) deteriorate due to heat generation during kneading.

In the present invention, the reaction temperature is 100 to 23.
0 ° C., and the reaction temperature is 15 ° C.
It is very preferable that the temperature is in the range of 0 to 220 ° C. In the present invention, the reaction pressure is preferably in the range of 0 to 2 MPa, and the reaction pressure is very preferably in the range of 0 to 1 MPa. As a method for producing the functionalized polyphenylene ether (a-2) of the present invention, the production is preferably performed using a paddle dryer as a reactor.

The functionalized polyphenylene ether (a-2) of the present invention can be efficiently produced by using a paddle dryer whose jacket temperature is set to a desired temperature. As the method for producing the functionalized polyphenylene ether (a-2) of the present invention, it is more preferable to produce the polyphenylene ether using a Henschel mixer as a reactor. When a Henschel mixer is used as the reactor, the polyphenylene ether (a-1) and the modifier (b) can be efficiently mixed and heated by shearing heat, so that the functionalized polyphenylene ether resin of the present invention can be efficiently used. Can be manufactured.

The functionalized polyphenylene ether (a-2) of the present invention can be produced by adding a reaction aid. The functionalized polyphenylene ether (a-2) of the present invention comprises a radical initiator,
Acids, bases, organic salts and inorganic salts are preferred. The functionalized polyphenylene ether (a-2) of the present invention has excellent color tone and appearance.

Styrene resin (B) used in the present invention
Is a polymer obtained by polymerizing a styrene compound or a compound copolymerizable with the styrene compound in the presence or absence of a rubbery polymer.

Specific examples of the styrene compound include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, pt
tert-Butylstyrene, ethylstyrene and the like can be mentioned, and styrene is most preferable. Examples of the compound copolymerizable with the styrene compound include methacrylates such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; and acid anhydrides such as maleic anhydride. And used together with styrenic compounds. The amount of the copolymerizable compound to be used is preferably 20% by weight or less, more preferably 15% by weight or less, based on the total amount with the styrene compound.

Examples of the rubbery polymer include a conjugated diene rubber, a copolymer of a conjugated diene and an aromatic vinyl compound, and an ethylene-propylene copolymer rubber. Specifically, polybutadiene and a styrene-butadiene copolymer are particularly preferred. When an unsaturated rubbery polymer is used, it is preferable to use a partially hydrogenated rubber. Specific examples of the styrene resin include polystyrene and rubber-reinforced polystyrene, styrene-acrylonitrile copolymer (AS resin), rubber-reinforced styrene-acrylonitrile copolymer (ABS resin), and other styrene copolymers. Can be Particularly preferred are polystyrene and rubber-modified polystyrene.

In the present invention, the mixing ratio of (A) the polyphenylene ether resin and (B) the styrene resin is 100/0 to 10/90 by weight, preferably 90/10.
３０30/70. Organopolysiloxanes generally used as flame retardants include four types of siloxane units (M unit: R ₃ SiO _0.5 , D unit: R ₂ SiO _1.0 , T unit: R
SiO _1.5 , Q unit: SiO _2.0 , wherein R represents a hydrogen or hydrocarbon group, respectively. ) Is a polymer consisting of any one or a combination thereof.

It is essential that the organopolysiloxane (C) used in the present invention contains a modified organopolysiloxane having at least one of an amino group, an imide group and an epoxy group as a molecular terminal group or a side chain group. The modified organopolysiloxane is used as a part or all of the organopolysiloxane (C). The number of amino groups bonded may be one or more in the organopolysiloxane molecule, preferably about 2 to 5, but may be more.

In the organopolysiloxane (C) used in the present invention, either the modified organopolysiloxane or the unmodified organopolysiloxane is represented by the formula R ₁ SiO _1.0 (D unit) among four types of siloxane units. Siloxane unit other than the unit, that is, the formula RSiO _1.5
(T units) and or SiO _2.0 (Q units), or R ₃ SiO ₀ as terminal groups. ₅ to contain an organopolysiloxane composed of siloxane units represented by (M units) it is essential.

In the present invention, all of RSiO
_1.5 organopolysiloxanes consisting (T units), or _{R 3 SiO 0,. 5 (} M units), an organopolysiloxane consisting of siloxane units represented by RSiO _1.5 (T units) and SiO _{2 .0} (Q units) Is preferably at least 20% by weight, preferably at least 50% by weight, and more preferably all of the organopolysiloxane used. Particularly preferred is
RSiO _1.5 (T units) or RSiO _1.5 (T units) and R ₃ SiO _0. An organopolysiloxane consisting of ₅ (M units).

The modified organopolysiloxane used in the present invention include, but are not necessarily comprised of the formula R ₁ SiO _1.0 (D unit) siloxane units other than the units represented by, preferably R ₃ SiO _{0. 5} ( M unit), RSi
It should be composed of O _1.5 (T units) and SiO _2.0 (Q units). An organopolysiloxane comprising a siloxane unit represented by the formula R ₁ SiO _1.0 (D unit) has little or no contribution to improving the flame retardancy.

The organopolysiloxane (C) used in the present invention has a weight average molecular weight of 400 to 50.
Less than 000, preferably 1,000 or more and 100,0
Less than 00, more preferably 2,000 or more and 10,000
It is less than 0. In the present invention, in all the organopolysiloxanes used, at least 20 mol%, preferably 30 to 90 mol%, of the bonded hydrocarbon groups in all the siloxane units represented by R have a phenyl group.
In addition, the terminal binding group other than the amino group is a hydroxyl group,
Either an alkoxy group or a hydrocarbon group is used. The modified organopolysiloxane having an amino group as a molecular terminal group is available from a silicone maker, and may be in a liquid or solid state at room temperature.

The amount of the organopolysiloxane (C) added is
0.1 to 15 with respect to 100 parts by weight of the total amount of the polyphenylene ether resin (A) and the styrene resin (B).
Parts by weight, preferably 0.5 to 10 parts by weight. In the present invention, the cyclic nitrogen compound (D) exhibits a synergistic effect when used in combination with the organopolysiloxane (C), and is used as needed to further improve the flame retardancy.

The cyclic nitrogen compound (D) of the present invention is a compound having a triazine skeleton containing no halogen or phosphorus in a molecule and a melamine derivative. Specific examples thereof include compounds having a triazine skeleton such as melamine, ammelide, ammeline, benzoguanamine, succinoguanamine, melamine cyanurate, melam, melem, meton, and melon, and sulfates thereof, and the like. , Meton and melon are more preferred, and melem is particularly preferred. The cyclic nitrogen compound (D) is
For the performance of the flame-retardant resin composition, a finely divided resin is preferred. The finely divided particle diameter is preferably one having an average particle diameter of 30 μm or less, more preferably 0.05 to 5 μm. Particles obtained by dispersing finely divided particles with a dispersant or lubricant such as a metal salt of higher fatty acid or fatty acid amide, or those subjected to surface treatment with a silane coupling agent, a titanium coupling agent, an aluminum chelating agent, etc. The invention flame retardant resin composition is more preferable in mechanical properties and surface appearance.

The combined use of the organopolysiloxane (C) and the cyclic nitrogen compound (D) not only prevents dripping at the time of combustion, but also drastically shortens the combustion time. Be demonstrated. Further, since the amount of addition can be suppressed, it is economically advantageous without sacrificing the inherent properties of the resin, and there is no generation of halogen gas or phosphine gas. it can. The addition amount of the cyclic nitrogen compound (D) is 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight based on 100 parts by weight of the total amount of the polyphenylene ether resin (A) and the styrene resin (B). is there.

The addition amount and the combination ratio of the organopolysiloxane (C) and the cyclic nitrogen compound (D) satisfy the mixing ratio of the polyphenylene ether resin (A) and the styrene resin (B) and the desired flame retardancy. The amount to be added may be appropriately selected, but should be limited as much as possible in consideration of the mechanical properties and economics of the composition. The polyether resin composition of the present invention is blended with an inorganic filler such as glass fiber, glass flake, kaolin clay, and talc, and other fibrous reinforcing agents, etc., and is a high-strength composite excellent in fluidity and heat resistance. You can get the body. Rubbery polymers such as styrene-butadiene block copolymers, styrene-isoprene block copolymers, and hydrogenated elastomers thereof are preferably used as impact modifiers.

To the polyether resin composition of the present invention, other additives such as a plasticizer, an antioxidant,
And stabilizers such as ultraviolet absorbers, antistatic agents, release agents,
Dyes and pigments or other resins can be added. Further, conventionally known various flame retardants and flame retardant assistants, for example, alkali metal hydroxides or alkaline earth metal hydroxides such as magnesium hydroxide and aluminum hydroxide containing water of crystallization, zinc borate compounds, It is possible to further improve the flame retardancy by adding a zinc stannate compound and further an inorganic silicon compound such as silica, kaolin clay and talc.

The method for producing the polyether resin composition of the present invention is not particularly limited, and the composition can be kneaded and manufactured using a kneading machine such as an extruder, a heating roll, a kneader, and a Banbury mixer. Among them, kneading with an extruder is preferable in terms of productivity. The kneading temperature may be in accordance with a preferable processing temperature of the base resin.
The range is from 00 to 360 ° C, preferably from 240 to 320 ° C. Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to the following examples.

The components used in the examples and comparative examples are as follows. (1) Polyphenylene ether The melting point of the polyphenylene ether is determined by measuring with a differential scanning calorimeter (DSC) and using the peak top temperature of a temperature-heat flow graph obtained when the temperature is increased at 20 ° C./min as the melting point. . PPE-1: poly 2,6-dimethyl-1,4-phenylene ether having a reduced viscosity ηsp / c measured in chloroform at 30 ° C. of 0.53 dl / g. The DSC measurement temperature-heat flow graph shows a single peak with a melting point of 2
It was 50 ° C.

PPE-2: Preparation of functionalized polyphenylene ether (a-2) 150 kg of polyphenylene ether (PPE-1) and 2 kg of maleic anhydride as a functional compound were heated to a jacket by the type of Henschel FM500 manufactured by Mitsui Mining Co., Ltd. Replace the inside of the mixer with nitrogen. The stirring blade is rotated at high speed, and the contents are heated to 200 ° C. over 50 minutes by shearing heat. After the jacket temperature reaches 200 ° C, 5
After continuing high-speed rotation for minutes, cool water is flowed through the jacket to cool.

50 g of the contents were collected and 100 m
Wash with 1 l of acetone and filter off using a glass filter. This operation is repeated five times to obtain the washed product 1 and the filtrate 1. As a result of gas chromatogram analysis of the filtrate 1, the amount of maleic anhydride was 0.25 g. A 20 g portion of the dried product 1 from the dried product 1 was washed with 40 ml of acetone, purified, and filtered using a glass filter. This operation is repeated five times to obtain the washed product 2 and the filtrate 2. As a result of gas chromatogram analysis of the filtrate 2, maleic anhydride was not included.

A film (film-b) was sandwiched between 1 g of the dried product-1 by sandwiching a polytetrafluoroethylene sheet, an aluminum sheet, and an iron plate in this order from the inside, using a press molding machine set to a temperature of 280 ° C. obtain. By the same operation, a film (film-a) is obtained from polyphenylene ether (PPE-1). For each of the obtained films, infrared spectroscopy is performed using a FT / IR-420 type Fourier transform infrared spectrophotometer manufactured by JASCO Corporation.

In the measurement for (film-b), 1
At 790 cm ⁻¹ , added to polyphenylene ether,
A peak derived from maleic anhydride is observed. The functionalized polyphenylene ether is designated as PPE-3. (2) Rubber Reinforced Polystyrene (HIPS) Rubber reinforced polystyrene having a rubber content of 12%, a ηsp / c of matrix polystyrene measured at 30 ° C. and a toluene solution of 0.64, and a volume average rubber particle diameter of 1.5 μm.

(3) Organopolysiloxane (Si-1): T unit of main chain structure is 100%, bonded phenyl group / methyl group = 70/30 (molar ratio), weight average molecular weight 3500, amino added to terminal Base equivalent 800m
g / g modified organopolysiloxane. (Si-2): the main chain structure is composed of D units and the terminals are M units, the viscosity at 25 ° C. is 750 centistokes, and the total equivalent of amino groups and alkoxy groups added to the terminals is 19
00 mg / g modified dimethylpolysiloxane. (Si-3): bonded phenyl group / methyl group = 70/3
0 (molar ratio), terminal OH about 3% by weight, weight average molecular weight 1
800, an unmodified organopolysiloxane containing 100% of T units having a main chain structure.

(Si-4): consisting of 55 mol% of T units and 45 mol% of M units, having a combined phenyl group / propyl group / methyl group = 37/18/45 (molar ratio) and a Jiro average molecular weight of 2500 Unmodified organopolysiloxane. (Si-5): An unmodified organopolysiloxane having a main chain structure of D units, a viscosity at 25 ° C. of 500 centistokes, and a combined phenyl group / methyl group = 70/30 (molar ratio). (Si-6): bonded phenyl group / methyl group = 45/6
5 (molar ratio), about 10% by weight of terminal methoxy, weight average molecular weight of 1700, T units and D units,
Unmodified organopolysiloxane with D units = 60/40 (molar ratio). (4) Cyclic nitrogen compound Melem having an average particle size of about 1.8 μm.

The physical properties of the resin compositions of Examples and Comparative Examples were evaluated by the following methods and conditions. (1) Flame retardancy Based on the UL-94 vertical combustion test, measurement was performed using an injection molded test piece having a thickness of 1/16 inch to evaluate the burning time and the presence or absence of dripping during burning. The level of flame retardancy is V-0
Is the most excellent, and is inferior in the ranks of V-1 and V-2, and is out of the rank when the burning time exceeds 30 seconds. (2) Heat resistance temperature The deflection temperature under load was measured at a load of 1.83 MPa based on ASTM D648, and was used as a measure of heat resistance. (3) Izod impact strength Measured based on ASTM D256.

[0052]

Examples 1 to 5 and Comparative Examples 1 to 7 The respective components were mixed in the proportions shown in Table 1 and supplied to a twin screw extruder having a maximum diameter of a heating cylinder of 300 ° C. and a screw diameter of 25 mm. The mixture was melt-kneaded at a rotation speed of 300 rpm, and the strand was cooled and cut to obtain a flame-retardant resin composition pellet. Next, a physical property test piece was formed from the obtained resin composition pellet by injection molding, and a physical property test was performed by the above-described test method. The results shown in Table 1 were obtained.

[0053]

[Table 1]

[0054]

According to the present invention, there is provided a flame-retardant resin composition which has a high level of flame retardancy without containing a halogen compound or a phosphorus compound, is environmentally preferable, and has excellent impact resistance and color tone.

Claims (12)

[Claims] 1. At least one carbon-carbon double bond or triple bond and at least one carbon-carbon double bond or triple bond in a molecular structure per 100 parts by weight of a polyphenylene ether (a-1) comprising a structural unit represented by the following formula (1): A mixture containing 0.01 to 10.0 parts by weight of a functionalized compound (b) having at least one of a carboxyl group, an acyl oxide group, and an imide group is added at room temperature to the melting point of the polyphenylene ether (a-1). The molecular weight is based on 100 parts by weight of the total amount of the polyphenylene ether resin (A) using a part or all of the functionalized polyphenylene ether (a-2) produced by reacting at the reaction temperature, and the styrene resin (B). An organopolysiloxane containing a modified organopolysiloxane having at least one of an amino group, an imide group and an epoxy group therein ( C) A flame-retardant polyether resin composition comprising 0.1 to 15 parts by weight and 0 to 15 parts by weight of a cyclic nitrogen compound (D). Embedded image [R ₁ and R ₄ are each independently hydrogen, halogen,
Represents a primary or secondary lower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy, provided that at least two carbon atoms separate a halogen atom from an oxygen atom; R ₂ ,
R ₃ is independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy, or halohydrocarbonoxy (provided that
At least two carbon atoms separating a halogen atom and an oxygen atom). ] 2. The polyphenylene ether (a-1) is
2. The flame-retardant flame-retardant powder according to claim 1, which comprises a powdery substance obtained by precipitation from a solution and having a functionalized polyphenylene ether (a-2) obtained by using a polyphenylene ether having a melting point of 240 to 260 [deg.] C. Polyether resin composition. 3. The reaction temperature with the functionalized compound (b) is 10
The functionalized polyphenylene ether (a-2) produced at 0 to 230 ° C is contained.
The flame-retarded polyether resin composition according to the above. 4. The reaction temperature with the functionalized compound (b) is 15
The flame-retardant polyether resin composition according to any one of claims 1 to 3, comprising a functionalized polyphenylene ether (a-2) produced in the range of 0 to 220 ° C. 5. The flame-retardant polyether resin composition according to claim 1, comprising a functionalized polyphenylene ether (a-2) produced using a paddle dryer. 6. The flame-retarded polyether resin composition according to claim 1, comprising a functionalized polyphenylene ether (a-2) produced using a Henschel mixer. 7. Functionalized polyphenylene ether (a-
The flame-retarded polyether resin composition according to any one of claims 1 to 6, wherein 2) is functionalized with an unsaturated carboxylic anhydride. 8. The mixing ratio of the polyphenylene ether resin (A) to the styrene resin (B) is 90/1 by weight.
The flame-retardant polyether resin composition according to any one of claims 1 to 7, wherein the ratio is from 0 to 30/70. 9. An organopolysiloxane (C) having the formula R
SiO _1.5 (T unit) and / or SiO _2.0 (Q unit)
The flame-retardant polyether resin composition according to any one of claims 1 to 8, comprising a siloxane unit represented by the following formula: 10. The organopolysiloxane (C) has the formula RSiO _1.5 (T units) and R ₃ Si as terminal bond.
The flame-retardant polyether resin composition according to any one of claims 1 to 8, comprising a siloxane unit represented by O _0.5 (M unit). 11. The organopolysiloxane (C) has 20 to 90 of the bonded hydrocarbon groups of all organopolysiloxanes.
The mole% is a phenyl group.
11. The flame-retarded polyether resin composition according to any one of 10. 12. The flame-retardant polyether resin composition according to claim 1, wherein the cyclic nitrogen compound (D) is melem.