JP2603029B2 - Low volatility flame retardant heat and impact resistant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition having excellent flame retardancy. More specifically, low volatility, flame retardancy,
The present invention relates to a resin composition having excellent fluidity, heat resistance and impact resistance.

[0002]

2. Description of the Related Art Thermoplastic resins are excellent in moldability and superior in impact resistance as compared with inorganic substances such as glass, so that they are widely used in automobile parts, home electric parts, OA equipment parts and the like. Has been used in the field. recent years,
For plastic materials used in such fields, demands for flame retardancy have been increasing due to safety issues, and various flame retardancy standards have been established. Various methods have been proposed as a method of imparting flame retardancy to a resin having high flammability, but very generally, a halogen compound such as a bromine compound having a high flame retardant effect, and if necessary, antimony oxide. Is added to the resin. As bromine compounds, nuclear bromine-substituted aromatic compounds such as tecabromodiphenyl ether, tetrabromobisphenol A, and brominated phthalimide are known, but the method by adding these flame retardants provides excellent flame retardancy. In addition, the impact strength and the heat distortion temperature are lowered, and in some cases, the flame retardant bleeds out to the surface of the resin molded product to cause a problem that the appearance of the molded product is deteriorated. Furthermore, during the molding of the resin, there are problems such as generation of gas harmful to the human body due to thermal decomposition of the halogen compound and corrosion of the mold and screw.

[0003] For this reason, methods for flame retardation without using a halogen compound have been studied. As such a method, a method of adding a hydrated metal compound such as aluminum hydroxide or magnesium hydroxide to a resin is known, but in order to obtain sufficient flame retardancy, a large amount of the hydrated metal compound is added. And the inherent properties of the resin are lost.

On the other hand, as a method not using such a hydrated metal compound, a flame-retardant resin composition comprising a nitrogen-containing compound selected from a vinyl aromatic resin, a polyphenylene ether, an organic phosphorus compound, a triazine and / or a derivative thereof is used. (JP-A-54-38348, JP-A-54-383)
49, European Patent No. 311,909), A
Flame-retardant resin composition obtained by blending red phosphorus, melamine, and thermo-crosslinking curable resin with BS resin
Publication). However, JP-A-54-38348, JP-A-54-38349, EP 311909, and JP-A-6
Although the resin composition described in the Japanese Patent Application Laid-Open No. 1-291643 is a useful flame-retardant resin material that does not use any halogen compound, it is mainly composed of polyphenylene ether having low fluidity. There was a problem of inferiority.

Furthermore, melamine, which is one of the triazine skeleton-containing compounds, has a problem that it has sublimability and adheres to a mold in powder form during injection molding (mold deposit).

[0006]

SUMMARY OF THE INVENTION In view of such circumstances, the present invention does not have the above-mentioned problems, that is, excellent low volatility, flame retardancy, good fluidity, heat resistance and impact resistance. It is an object of the present invention to provide a resin composition which has been obtained.

[0007]

Means for achieving the object] The present inventors have carried out intensive investigations and found that the low volatility of the flame retardant resin composition, conventional (A) port
Polystyrene thermoplastic resin, rubber modified styrene resin
Surprisingly, the combination of a polymer blend with polyphenylene ether and (B) a hydroxyl group-containing aromatic phosphate flame retardant with (C) a triazine skeleton-containing compound having a specific thermal stability results in a surprising flame retardancy. The inventors have found that it is possible to dramatically improve the volatility resistance while maintaining the properties, good fluidity, heat resistance and impact resistance, and have reached the present invention.

That is, the present invention relates to (A) a polystyrene-based heat
Plastic resin, rubber-modified styrene resin and polyphenylene
50 to 80% by weight of a polymer blend with ether ,
(B) hydroxy represented by the following general formulas (2) and (3)
A resin composition containing from 1 to 45% by weight of an aromatic phosphate ester having a hydroxyl group and from 1 to 30% by weight of a compound containing a triazine skeleton (C), wherein thermal decomposition of the compound containing a triazine skeleton (C) is carried out. A low-volatility flame-retardant heat-resistant impact resistance, characterized in that the temperature at which the weight is reduced by 10% by weight is 300 ° C. or more in a heating test in air (heating rate 10 ° C./min), which is an index of temperature. It is a resin composition.

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Embedded image (However, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , A
r ₆ is a phenyl group, a xyenyl group, an ethylphenyl group,
Selected from isopropylphenyl and butylphenyl groups
(B) at least in the phosphate ester
Also, one hydroxyl group is substituted with the above aromatic group.
You. N represents an integer of 0 to 3, and m is an integer of 1 or more.
Represents a number. )

Hereinafter, the present invention will be described in detail. The resin composition of the present invention comprises (A) a polystyrene-based thermoplastic resin,
Of polystyrene-modified resin and polyphenylene ether
Limmer blend , (B) represented by general formulas (2) and (3)
The present invention cannot achieve the object of the invention if any of them contains a hydroxyl group-containing aromatic phosphate ester and a (C) triazine skeleton-containing compound having a specific thermal stability. The component (A) serves as a main component of the molding resin composition, and plays a role in maintaining the strength of the molded article. The component (B) together with the component (C) imparts flame retardancy to the component (A). It is a component for.

[0010] Here, the component (C) acts as a flame retardant aid of the component (B).
(0 ° C./min), the temperature at which the weight is reduced by 10% by weight is 3
It is essential that the temperature be at least 00 ° C. When a triazine skeleton-containing compound having a temperature of less than 300 ° C. is used, a metal mold adheres to the powder during injection molding. The component (A) of the present invention
As the thermoplastic resin, a polystyrene-based thermoplastic resin,
Between rubber-modified styrene resin and polyphenylene ether
Polymer blends are exemplified.

The rubber-modified styrene resin as the component (A) of the present invention refers to a graft polymer in which a rubbery polymer is dispersed in a matrix of a vinyl aromatic polymer in the form of particles. A known bulk polymerization, bulk suspension polymerization, solution polymerization, or a monomer mixture by adding an aromatic vinyl monomer and, if necessary, a copolymerizable vinyl monomer in the presence of the polymer, It is obtained by emulsion polymerization.

Examples of such resins include impact-resistant polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acryl rubber-styrene copolymer), and AES resin (acrylonitrile-ethylene copolymer). Propylene rubber-styrene copolymer). Here, the rubber-like polymer needs to have a glass transition temperature (Tg) of −30 ° C. or less, and if it exceeds −30 ° C., the impact resistance decreases.

Examples of such rubbery polymers include diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), and saturated rubbers obtained by hydrogenating the diene rubbers, isoprene rubbers and chloroprene rubbers. , An acrylic rubber such as polybutyl acrylate, and an ethylene-propylene-diene monomer terpolymer (EPDM). A diene rubber is particularly preferred.

The aromatic vinyl monomer as an essential component in the graft-polymerizable monomer mixture to be polymerized in the presence of the rubbery polymer includes, for example, styrene, α-methylstyrene, paramethylstyrene, p-chlorostyrene, p-
Bromostyrene, 2,4,5-tribromostyrene and the like are most preferred, but styrene may be the main component and other aromatic vinyl monomers described above may be copolymerized.

If necessary, one or more monomer components copolymerizable with the aromatic vinyl monomer can be introduced as components of the rubber-modified styrenic resin. When it is necessary to increase oil resistance, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used. When it is necessary to lower the melt viscosity at the time of blending, an acrylate having an alkyl group having 1 to 8 carbon atoms can be used. Further, when it is necessary to further increase the heat resistance of the polymer composition, α-
Monomers such as methylstyrene, acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide may be copolymerized. The content of the vinyl monomer copolymerizable with the vinyl aromatic monomer in the monomer mixture is from 0 to 40% by weight.

The rubbery polymer in the rubber-modified styrenic resin of the present invention is preferably from 5 to 80% by weight, particularly preferably from 10 to 50% by weight, and the graft-polymerizable monomer mixture is preferably from 95 to 20% by weight. %, More preferably in the range of 90 to 50% by weight. Outside this range, the balance between impact resistance and rigidity of the desired polymer composition cannot be obtained. Furthermore, the rubber particle diameter of the styrene polymer is
0.1 to 5.0 μm is preferable, and 0.2 to 3.0 μm is particularly preferable.
m is preferred. Outside the above range, the impact resistance tends to decrease.

The polyphenylene ether (hereinafter abbreviated as PPE) as the component (A) of the present invention is a homopolymer and / or a copolymer comprising a bonding unit represented by the following formula.

[0018]

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However, R ₁ , R ₂ , R ₃ , and R ₄ are each selected from the group consisting of hydrogen, hydrocarbon, and substituted hydrocarbon groups, and may be the same or different. Specific examples of this PPE include poly (2,
6-dimethyl-1,4-phenylene ether, 2,6-
Copolymers of dimethylphenol and 2,3,6-trimethylphenol are preferred, and among them, poly (2,6-
Dimethyl-1,4-phenylene ether) is preferred.
The method for producing such PPE is not particularly limited. For example, a complex of a cuprous salt and an amine according to the method described in U.S. Pat. No. 3,306,874 is used as a catalyst, and for example, 2,6-xylenol Can be easily produced by oxidative polymerization of the compound. In addition, US Pat. No. 3,306,875 and US Pat.
7,357, U.S. Pat. No. 3,257,358, Japanese Patent Publication No. 52-17880,
It can be easily produced by the method described in JP-A-51197. The reduced viscosity of the PPE used in the present invention (0.5 g
/ Deciliter, chloroform solution, measured at 30 ° C)
Is preferably in the range of 0.20 to 0.7 deciliter / g, and more preferably in the range of 0.30 to 0.60 deciliter / g. Means for satisfying the above-mentioned requirement regarding the reduced viscosity of PPE include adjustment of the amount of catalyst in the production of PPE.

[0020]

[0021] In the present invention component (B) is a hydroxyl-containing aromatic phosphate esters, different component (B)
May be used in combination with the organic phosphorus compound.

[0022]

[0023]

The present invention is represented by the above general formulas (2) and (3).
Among the (B) hydroxyl group-containing aromatic phosphates to be used, diphenylresorcinyl phosphate of the following formula is particularly preferable.
-223158, phenol,
Obtained by the reaction of hydroxyphenol, aluminum chloride and phosphorus oxychloride.

[0025]

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[0026]

The triazine skeleton-containing compound of the component (C) of the present invention is represented by (B) the general formulas (2) and (3).
(B) A component for further improving the flame retardancy as a flame retardant aid of a hydroxyl group-containing aromatic phosphate ester, and has a heat resistance in air of 10 ° C./min. It is essential that the temperature at which the weight% is reduced is 300 ° C. or higher. When the temperature is lower than 300 ° C., the triazine skeleton-containing compound adheres to the mold during injection molding, and the industrial use is narrowed.

Specific examples of the triazine skeleton-containing compound of the component (C) of the present invention include melamine cyanurate (formula 5), melamine phosphate (formula 6), melam (formula 7), and melem (formula 8) represented by the following formulas. ), Melon (a product of deammonification of three to three molecules of melem at 600 ° C. or higher), succinoguanamine (formula 9), melamine resin (formula 10), BT resin (formula 11), and the like.

[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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When it is necessary to improve the fluidity of the resin composition of the present invention, (D) a higher fatty acid amide compound can be blended, which comprises a higher fatty acid,
It is a reaction product with (a) diamines or (b) amino alcohols. Here, the higher fatty acids are those having 11 to 2 carbon atoms.
It is a fatty acid having one alkyl group or alkenyl group, and stearic acid is particularly preferable.

The above diamines have 2 to 10 carbon atoms.
And particularly preferred is ethylenediamine. Further, the amino alcohols are hydrocarbon amino alcohols having 2 to 10 carbon atoms, such as monoethanolamine, 3-amino-1-propanol, and 4-amino-1-butanol.

The higher fatty acid amide compound (D) of the present invention is particularly preferably ethylene bisstearylamide, which improves the fluidity while maintaining flame retardancy, heat resistance and impact resistance. Let it. (A) constituting the resin composition of the present invention
Thermoplastic resin and (B) hydroxyl group-containing aromatic phosphoric acid
Regarding the quantitative ratio of the ester flame retardant, the (C) triazine skeleton-containing compound and the (D) higher fatty acid amide compound,
(A) is 50 to 80% by weight, (B) is 1 to 45% by weight.
(C) is preferably in the range of 1 to 30% by weight, and (D) is preferably in the range of 0 to 20% by weight. Outside the above range, volatility resistance,
Flame retardancy, impact resistance, heat resistance and fluidity tend to be unbalanced.

The resin composition of the present invention can be obtained by, for example, melt-kneading the above components with a commercially available single-screw extruder or twin-screw extruder or the like. In this case, an antioxidant such as BHT is used. A UV absorber, a tin-based heat stabilizer, a flame retardant, a lubricant such as stearic acid and zinc stearate, a filler, a reinforcing agent, a dye, a pigment, and the like can be added as necessary.

By subjecting the composition of the present invention thus obtained to, for example, injection molding or extrusion molding, a molded article having excellent volatility resistance, flame retardancy, fluidity, impact resistance and heat resistance can be obtained. can get.

[0041]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention. In addition, the measurement in an Example and a comparative example was performed using the following method or measuring equipment. (1) Rubber weight average particle diameter: The weight average particle diameter of the rubber-modified styrenic resin was determined by calculating the butadiene polymer particle diameter in a transmission electron micrograph taken by an ultrathin section method of the resin composition, and It is calculated by:

Weight average particle diameter = ΣNi · Di ⁴ / ΣNi · Di ³ (where Ni is the number of butadiene-based polymer particles having a particle diameter of Di.) (2) Reduced viscosity ηsp / c rubber modified Methyl ethyl ketone 18 per gram of styrene resin
A mixed solvent of 2 ml of methanol and 2 ml of methanol was added, and the mixture was shaken at 25 ° C for 2 hours.
And centrifuge for 30 minutes. The supernatant was taken out and the resin component was precipitated with methanol and then dried.

0.1 g of the resin thus obtained was dissolved in toluene to form a solution having a concentration of 0.5 g / deciliter, and 10 ml of this solution was placed in a Cannon-Fenske viscometer at 30 ° C. The number of seconds t ₁ was measured. On the other hand, using the same viscometer, the number of seconds t
₀ was measured and calculated by the following equation. ηsp / c = {t ₁ / (t ₀ -1)} / c (C: polymer concentration g / deciliter) (3) Volatility Using a Shimadzu thermal analyzer DT-40, under an air stream, 10
The temperature at which the temperature was raised at 10 ° C./min and the weight loss was 10% by weight was used as a measure of the volatility of the composition. (4) Izod impact strength: measured at 23 ° C. by a method based on ASTM-D256. (V notch, 1/8 inch test piece) (5) Vicat softening temperature: Measured by a method in accordance with ASTM-D1525 and used as a measure of heat resistance. (6) Melt flow rate (MFR): Measured by a method in accordance with ASTM-D-1238 as an index of fluidity. It was determined from the extruded amount per 10 minutes (g / 10 min.) Under the conditions of a load of 5 kg and a melting temperature of 200 ° C. (7) Flame retardancy and drip properties VB (Vertical Bur) conforming to UL-94
(1/8 inch and 1/1)
Evaluation on a 2-inch test piece).

[0044]

Example 1 (a) Production of thermoplastic resin Production of rubber-modified styrene resin (HIPS) Polybutadiene [(cis 1,4 bond / trans 1,4 bond / vinyl 1,2 bond weight ratio = 95/2 / 3) (Nipol 1220SL, trade name, manufactured by Zeon Corporation)]
Was dissolved in the following mixture to give a uniform solution.

Polybutadiene 10.5% by weight Styrene 74.2 {Ethylbenzene 15.0} α-Methylstyrene dimer 0.27 {1,1-bis (t-butylperoxy) -3,3,5-trimethyl Cyclohexane 0.03〃 Next, the above-mentioned mixed solution was continuously sent to an in-line four-stage reactor equipped with a stirrer, and the first stage was stirred at 190 rpm and 126 rpm.
° C, the second stage is 50 rpm, 133 ° C, the third stage is 20 rpm
m, 140 ° C., the fourth stage was carried out at 20 rpm and 155 ° C. Subsequently, the polymerization liquid having a solid content of 73% was led to a devolatilizer to remove unreacted monomers and a solvent to obtain a rubber-modified styrene resin (referred to as HIPS-1). As a result of analyzing the obtained rubber-modified styrene resin, the rubber content was 14
% By weight, the weight average particle diameter of the rubber was 2.4 μm, and the reduced viscosity ηsp / c was 0.53 deciliter / g.

Polystyrene (GPPS) Commercially available polystyrene [Stylon 680 (referred to as GPPS) manufactured by Asahi Chemical Industry Co., Ltd.] was used. Manufacture of polyphenylene ether (PPE) After sufficiently replacing the inside of a stainless steel reactor having an oxygen inlet at the bottom of the reactor with a cooling coil and stirring blades with nitrogen, 54.8 g of cupric bromide. , Di-n-
1110 g of butylamine and 20 liters of toluene,
8.75 kg of 2,6-xylenol was dissolved in a mixed solvent of 16 liters of n-butanol and 4 liters of methanol and charged into the reactor. Oxygen was continuously blown into the reactor while stirring, and polymerization was carried out for 180 minutes while controlling the internal temperature to 30 ° C. After completion of the polymerization, the precipitated polymer was separated by filtration. A mixed solution of methanol / hydrochloric acid was added thereto to decompose the remaining catalyst in the polymer, and the polymer was sufficiently washed with methanol and dried to obtain a powdery polyphenylene ether (referred to as PPE). The reduced viscosity was 0.55 deciliter / g.

Further, this PPE and polystyrene (Stylon 685, trade name, manufactured by Asahi Kasei Corporation) were used in a weight ratio of 7%.
The mixture was mixed at 0/30 and melt-extruded at 350 ° C. using a twin-screw extruder. The resulting pellet is called PPE-MB. (B) Preparation of an organic phosphorus compound (organic phosphorus compound containing a hydroxyl group-containing aromatic phosphate ester) 122.7 parts by weight (molar ratio 2.0) of phenol, 0.87 parts by weight of aluminum chloride (molar ratio 0) .01) was placed in a flask, and 100 parts by weight of phosphorus oxychloride (molar ratio: 1.0) was added dropwise at 90 ° C. over 1 hour. 71.7 parts by weight of resorcinol (molar ratio 1.0) was added to the resulting intermediate to further react. In order to complete the reaction, the temperature was gradually raised and finally raised to 180 ° C. to complete the esterification. Next, the reaction product was cooled and washed with water to remove the catalyst and chlorine, thereby obtaining a phosphoric ester mixture (hereinafter referred to as FR). When this mixture was analyzed by GPC (gel permeation chromatography), diphenylresorcinyl phosphate (hereinafter referred to as TPP-OH) represented by the following formula 4 and triphenyl phosphate (hereinafter referred to as TPP) represented by the following formula 12 were obtained. ) And a condensed aromatic phosphate (hereinafter referred to as TPP dimer)
And a weight ratio of 54.2 / 18.3 / 2, respectively.
7.5.

[0048]

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[0049]

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(C) Triazine skeleton-containing compound A commercially available melamine cyanurate as a triazine skeleton-containing compound [MC610 (MC, manufactured by Nissan Chemical Industries, Ltd.)
)] Was used. The temperature at which the MC lost 10% by weight was 351.8 ° C. (D) Higher fatty acid amide As higher fatty acid amide, commercially available ethylene bisstearylamide (trade name, Kao Wax EB FF, manufactured by Kao Corporation)
(Referred to as EBS)｝. (E) Preparation and evaluation of composition HIPS-1 / GPPS / PPE-MB / FR / M
50/21/29/18/14 / by weight ratio of C / EBS
The mixture was mechanically mixed at a ratio of 2 and the melting temperature was 250 ° C. and the number of rotations was 50 rpm using a lab plast mill manufactured by Toyo Seiki Seisaku-sho, Ltd.
For 5 minutes. From the polymer composition thus obtained, a 1/8 inch thick test piece was prepared by a hot press and evaluated for flame retardancy, volatile Vicat softening temperature, Izod impact strength, and melt flow rate (MFR). Was done. Table 1 shows the results.

On the other hand, the above-mentioned resin composition is added to a resin having a thickness of 30 mm.
φ twin screw extruder (Model AS3 manufactured by Nakatani Machinery Co., Ltd.)
In 0), the mixture was melt-extruded at 260 ° C. to produce pellets. The pellets thus obtained were subjected to an injection molding machine (model IS80A, manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 230.
C., the mold temperature was 20.degree. C., the injection time was 10 seconds, and the cooling time was 15 seconds. The mold surface was observed after 50 shots. As shown in Table 1, when the resin composition of the present invention was used, no deposit was observed on the mold surface.

[0052]

Example 2 (A) Preparation of Triazine Skeleton-Containing Compound (SG) 100 parts by weight of succinonitrile (NC (CH ₂ ) ₂ CN) (molar ratio 1) and 231 parts by weight of dicyandiamide represented by the following formula (13) Ratio 2.2) and 1690 parts by weight of polyethylene glycol monoethyl ether were placed in a flask and dissolved by heating at 115 to 124 ° C (solution I). on the other hand,
25.4 parts by weight of 85% by weight potassium hydroxide were added to 185 parts by weight of polyethylene glycol monoethyl ether.
The solution dissolved at 0 ° C. was added dropwise to the above solution I in 10 to 15 minutes, and the mixture was reacted at 120 to 124 ° C. for 3 hours to precipitate crystals.

[0053]

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Next, the reaction solution was filtered while hot at 80 to 90 ° C., further sufficiently washed with polyethylene glycol monoethyl ether, pulverized with a homogenizer, and vacuum dried. The yield of succinoguanamine (hereinafter referred to as SG) represented by the following formula 9 was 9
0.0%. The temperature at which the SG was reduced by 10% by weight was 391.9 ° C.

[0055]

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(B) Preparation and Evaluation of Composition The same experiment as in Example 1 was repeated, except that the above SG was used instead of MC. Table 1 shows the results.

[0057]

Example 3 (a) Triazine skeleton-containing compound (Melem) As a triazine skeleton-containing compound, melem (manufactured by Nissan Chemical Industries, Ltd.) obtained by a thermal decomposition reaction of melamine represented by the following formula 14 was used. The weight loss temperature of the above melem at 10% by weight was 369.3 ° C.

[0058]

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(B) Preparation and Evaluation of Composition The same experiment as in Example 1 was repeated, except that the above-mentioned melem was used in place of MC. Table 1 shows the results.

[0060]

Example 4 (a) Triazine Skeleton-Containing Compound (Melon) Melon (manufactured by Nissan Chemical Industries, Ltd.) obtained by a thermal decomposition reaction of melamine was used as a triazine skeleton-containing compound. The 10% weight loss temperature of the above melon was 522.1.
° C. (B) Preparation and evaluation of composition In Example 1, the same experiment as in Example 1 was repeated, except that the melon was used instead of MC. Table 1 shows the results.

[0061]

Comparative Example 1 The same experiment as in Example 1 was repeated except that MC was not used. Table 1 shows the results. According to Table 1, it can be seen that the flame retardancy is inferior unless a triazine skeleton-containing compound is used.

[0062]

Comparative Example 2 (a) Triazine Skeleton-Containing Compound (Melamine) As the triazine skeleton-containing compound, a commercially available melamine (manufactured by Mitsui Toatsu Chemicals, Inc. (referred to as ML)) was used. The melamine had a weight loss temperature of 106.4% by weight. (B) Preparation and Evaluation of Composition In Example 1, the same experiment as in Example 1 was repeated, except that the above ML was used instead of MC. Table 1 shows the results. Also, as shown in Table 1, when melamine was used as the triazine skeleton-containing compound, a large number of white powders adhered to the mold surface during injection molding.

[0063]

Example 5 In Example 1, the resin composition was changed to HIPS.
-1 / PPE-MB / FR / MC / EBS = 74/26
Example 1 except for changing to / 19/15 (weight ratio)
The same experiment was repeated. Table 1 shows the results.

[0064]

Example 6 In Example 1, the resin composition was changed to HIPS.
-1 / PPE-MB / FR / MC / EBS = 77/23
The same experiment as in Example 1 was repeated, except that the ratio was changed to / 19/15/2 (weight ratio). Table 1 shows the results.

[0065]

Example 7 The same experiment as in Example 5 was repeated, except that SG was used instead of MC.
Table 1 shows the results.

[0066]

Example 8 The same experiment as in Example 6 was repeated, except that SG was used instead of MC.
Table 1 shows the results.

[0067]

Example 9 (A) Rubber-Modified Styrenic Resin In the production of HIPS-1 in Example 1, mineral oil (liquid paraffin) (trade name Smoyl PS-260, manufactured by Matsumura Petroleum Institute Co., Ltd.) was used as a resin component. The same polymerization as that of HIPS-1 was carried out except that 2% by weight was added.
(Referred to as HIPS-2) (b) Phosphorus-containing flame retardant As the phosphorus-containing flame retardant, red phosphorus powder [produced by Rin Kagaku Kogyo Co., Ltd. under the trade name of Nova Excel 150 (RP and (C) Preparation and evaluation of composition In Example 1, the resin composition was prepared using the above-described HIPS-2 / P.
PE-MB / FR / RP / MC / EBS = 80/20 /
The same experiment as in Example 1 was repeated except that the ratio was changed to 20 / 0.8 / 16/2 (weight ratio). Table 1 shows the results.

[0068]

[Table 1]

[0069]

The resin composition of the present invention is a resin composition excellent in low volatility, flame retardancy, good fluidity, heat resistance and impact resistance. This composition is suitable for home electric appliance parts, OA equipment parts, etc., and has no volatilization, so that there is no mold adhesion at the time of injection molding, and plays a large role in these industries.

Claims (1)

(57) [Claims] 1. A polystyrene-based thermoplastic resin (A)
Of polystyrene-modified resin and polyphenylene ether
Rimmer blend is 50 to 80 wt%, (B) the following general formula (2), hydroxyl group-containing aromatic represented by (3)
A resin composition containing 1 to 45% by weight of a phosphate ester and 1 to 30% by weight of a (C) triazine skeleton-containing compound, and is an index of the thermal decomposition temperature of the (C) triazine skeleton-containing compound. Heating test in air (heating rate 10
℃ / min), the temperature at which the weight is reduced by 10% by weight is 30
A low-volatile flame-retardant heat-resistant impact-resistant resin composition characterized by being at least 0 ° C. Embedded image Embedded image (However, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , Ar ₅ , A
r ₆ is a phenyl group, a xyenyl group, an ethylphenyl group,
Selected from isopropylphenyl and butylphenyl groups
(B) at least in the phosphate ester
Also, one hydroxyl group is substituted with the above aromatic group.
You. N represents an integer of 0 to 3, and m is an integer of 1 or more.
Represents a number. )