JPH05339417A - Low-volatile flame-retardant resin composition resistant to heat and impact - Google Patents

Abstract

PURPOSE:To provide the subject resin composition excellent in low volatility, flame retardancy, good fluidity, heat resistance and impact resistance. CONSTITUTION:The objective resin composition comprising (A) a thermoplastic resin, (B) a phosphorus-contg. flame retardant, an organophosphorus compound and/or red phosphorus, and (C) a triazine skeleton-contg. compound having a specific thermal decomposition temperature.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION 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 flowability, heat resistance and impact resistance.

[0002]

2. Description of the Related Art Thermoplastic resins are superior in moldability as compared with inorganic materials such as glass, and are also excellent in impact resistance, so that they can be used in a wide variety of fields including automobile parts, home electric appliance parts, and OA equipment parts. Has been used in the field of. recent years,
Due to safety concerns, the demand for flame retardancy is increasing for plastic materials used in such fields, and various flame retardancy standards have been established. Various methods have been proposed as a method for imparting flame retardancy to a resin that is easily flammable, but in general, halogen compounds such as bromine compounds having a high flame retardant effect, and antimony oxide if necessary. 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 gives excellent flame retardancy. However, the impact strength and the heat distortion temperature are lowered, and in some cases, the flame retardant bleeds out on the surface of the resin molded product to deteriorate the appearance of the molded product. Furthermore, when the resin is molded, the halogen compounds are thermally decomposed to generate a gas harmful to the human body, and the mold and the screw are corroded.

For this reason, methods of flame retarding without using halogen compounds have been investigated. 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 above hydrated metal compound is added. However, there is a drawback that the original characteristics 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 vinyl aromatic resin, polyphenylene ether, organic phosphorus compound, triazine and / or its derivative. (JP-A-54-38348, JP-A-54-383)
49, European Patent No. 311,909), A
Flame-retardant resin composition obtained by blending BS resin with red phosphorus, melamine, and a heat-crosslinking curable resin (JP-A-61-291643).
Issue). However, the above-mentioned JP-A-54-38348, JP-A-54-38349, European Patent No. 311,909, and JP-A-6-36908.
The resin compositions described in JP-A 1-2911643 are useful flame-retardant resin materials that do not use halogen compounds, but since they mainly contain polyphenylene ether having low fluidity, the moldability of the resin composition is low. There was the problem of being inferior.

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

[0006]

In view of the above situation, the present invention does not have the above-mentioned problems, that is, low volatility, flame retardancy, good flowability, heat resistance and impact resistance. Another object of the present invention is to provide a resin composition.

[0007]

Means for Achieving the Object The inventors of the present invention have diligently studied to reduce the volatility of a flame-retardant resin composition, and as a result, compared with the conventional (A) thermoplastic resin and (B) phosphorus-containing flame retardant, By combining the (C) triazine skeleton-containing compound having a specific thermal stability, surprisingly, flame retardancy, good flowability,
The inventors have found that it is possible to dramatically improve volatility while maintaining heat resistance and impact resistance, and have reached the present invention.

That is, the present invention provides (A) a thermoplastic resin,
A resin composition comprising (B) an organic phosphorus compound and / or a phosphorus-containing flame retardant that is red phosphorus, and (C) a triazine skeleton-containing compound, wherein (C) an index of the thermal decomposition temperature of the triazine skeleton-containing compound. In a heating test in air (heating rate of 10 ° C./min), a low-volatile flame-retardant thermal shock-resistant resin composition having a temperature of 300 ° C. or higher when reducing 10% by weight. Is.

The present invention will be described in detail below. The resin composition of the present invention contains (A) a thermoplastic resin, (B) a phosphorus-containing flame retardant, and (C) a triazine skeleton-containing compound having a specific thermal stability, and any one of which is absent. Can not achieve the purpose of. The component (A) constitutes the main component of the molding resin composition and plays a role of maintaining the strength of the molded product, and the component (B) imparts flame retardancy to the component (A) together with the component (C). It is an ingredient for.

Here, the component (C) acts as a flame retardant aid for the component (B), but a heating test in air (heating rate 1
At 0 ° C / min), the temperature when reducing 10% by weight is 3
It is essential that the temperature is 00 ° C. or higher. If a triazine skeleton-containing compound having a temperature of less than 300 ° C. is used, the powder adheres to the mold during injection molding. The thermoplastic resin as the component (A) of the present invention is a thermoplastic resin such as polystyrene type, polyolefin type, polyvinyl chloride type, polyphenylene ether type, polyamide type, polyester type, polyphenylene sulfide type, polycarbonate type or polymethacrylate type. It is a resin. Here, a polystyrene-based thermoplastic resin is particularly preferable as the thermoplastic resin, and a polymer blend of a rubber-modified styrene-based resin and polyphenylene ether is more preferable.

The rubber-modified styrenic resin as the component (A) of the present invention is a graft polymer in which a rubber-like polymer is dispersed in particles in a matrix composed of a vinyl aromatic polymer. Known monomer bulk polymerization, bulk suspension polymerization, solution polymerization, or a mixture of aromatic vinyl monomer and vinyl monomer copolymerizable with aromatic vinyl monomer in the presence of a polymer. It is obtained by emulsion polymerization.

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

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

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

If necessary, one or more monomer components copolymerizable with the aromatic vinyl monomer may be introduced as a component of the rubber-modified styrene resin. When it is necessary to enhance oil resistance, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used. When it is necessary to reduce the melt viscosity at the time of blending, an acrylate ester composed of 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 0 to 40% by weight.

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

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

[0018]

[Chemical 1]

However, R ₁ , R ₂ , R ₃ and R ₄ are each selected from the group consisting of hydrogen, hydrocarbons and substituted hydrocarbon groups and may be the same or different from each other. As a concrete example of this PPE, poly (2,
6-dimethyl-1,4-phenylene ether, 2,6-
Copolymers of dimethylphenol and 2,3,6-trimethylphenol are preferable, and among them, poly (2,6-
Dimethyl-1,4-phenylene ether) is preferred.
The method for producing such PPE is not particularly limited, and for example, a complex of a cuprous salt and an amine obtained by the method described in US Pat. No. 3,306,874 is used as a catalyst, and, for example, 2,6 xylenol is used. Can be easily produced by oxidatively polymerizing the above compounds. In addition, US Pat. No. 3,306,875 and US Pat. No. 3,25
No. 7,357, U.S. Pat. No. 3,257,358, Japanese Patent Publication No. 52-17880, and Japanese Patent Laid-Open No. 50-88.
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, 30 ℃ measurement)
Is preferably in the range of 0.20 to 0.7 deciliter / g, more preferably in the range of 0.30 to 0.60 deciliter / g. Examples of means for satisfying the above requirements regarding the reduced viscosity of PPE include adjustment of the amount of catalyst during the production of PPE.

The component (B) of the present invention is a phosphorus-containing flame retardant which is an organic phosphorus compound and / or red phosphorus. The organic phosphorus compound, for example, phosphine, phosphine oxide, biphosphine, phosphonium salt, phosphinate,
Examples thereof include phosphoric acid ester and phosphorous acid ester. More specifically, triphenyl phosphate,
Methyl neopentyl phosphite, pentaerythritol diethyl diphosphite, methyl neopentyl phosphonate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate, dicyclopentyl hypophosphite, dineopentyl hypophosphite, phenylpyrocatecholphosphite Examples thereof include phyto, ethylpyrocatechol phosphate, dipyrocatechol hyposiphosphate and the like.

Here, a hydroxyl group-containing aromatic phosphate ester is particularly preferable, and it may be used in combination with the above-mentioned organic phosphorus compound having no hydroxyl group. The above-mentioned hydroxyl group-containing aromatic phosphoric acid ester is a phosphoric acid ester containing one or more phenolic hydroxyl groups in tricresyl phosphate, triphenyl phosphate, condensed phosphoric acid ester thereof or the like, For example, the following compounds.

[0022]

[Chemical 2]

[0023]

[Chemical 3]

(However, Ar ₁ , Ar ₂ , Ar ₃ and A
r ₄ , Ar ₅ and Ar ₆ are aromatic groups selected from a phenyl group, a xylenyl group, an ethylphenyl group, an isopropylphenyl group and a butylphenyl group, and at least one hydroxyl group is contained in the (B) phosphate ester. It is substituted with the above aromatic group. Further, n represents an integer of 0 to 3, and m represents an integer of 1 or more. ) Among the above-mentioned hydroxyl group-containing aromatic phosphoric acid esters of the present invention, diphenylresorcinyl phosphate of the following formula is particularly preferable, and its production method is disclosed in, for example, JP-A-1-223158, and phenol , Hydroxyphenol, aluminum chloride and phosphorus oxychloride.

[0025]

[Chemical 4]

The red phosphorus in the component (B) of the present invention is
In addition to general red phosphorus, its surface is previously coated with a metal hydroxide film selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide, aluminum hydroxide, and hydroxide. A metal hydroxide selected from magnesium, zinc hydroxide, and titanium hydroxide, and a metal coating selected from thermosetting resins, a metal selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide, and titanium hydroxide. A double-coated thermosetting resin film on a hydroxide film can also be preferably used.

The triazine skeleton-containing compound of the component (C) of the present invention is a component for further improving the flame retardancy as a flame retardant aid of the phosphorus-containing flame retardant (B), and a heating test in air. At the temperature rising rate of 10 ° C./min, it is essential that the temperature when reducing the amount by 10% by weight is 300 ° C. or higher.
If the temperature is lower than 300 ° C., the triazine skeleton-containing compound adheres to the mold during injection molding, narrowing the industrial use.

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). ), Melon (a product of deammonification of 3 molecules of melem at 600 ° C. or higher), succinoguanamine (formula 9), melamine resin (formula 10), and BT resin (formula 11).

[0029]

[Chemical 5]

[0030]

[Chemical 6]

[0031]

[Chemical 7]

[0032]

[Chemical 8]

[0033]

[Chemical 9]

[0034]

[Chemical 10]

[0035]

[Chemical 11]

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 added, which comprises a higher fatty acid and
It is a reaction product with (a) diamines or (b) amino alcohols. Here, the higher fatty acid has 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-mentioned diamines have 2 to 10 carbon atoms.
Of the above hydrocarbon diamines, and ethylenediamine is particularly preferable. Further, the above-mentioned amino alcohols are hydrocarbon amino alcohols having 2 to 10 carbon atoms, and examples thereof include monoethanolamine, 3-amino-1-propanol and 4-amino-1-butanol.

As the higher fatty acid amide compound as the component (D) of the present invention, ethylene bis stearyl amide is particularly preferable, and the fluidity is improved while maintaining flame retardancy, heat resistance and impact resistance. Let (A) which constitutes the resin composition of the present invention
Regarding the amount ratio of the thermoplastic resin, (B) phosphorus-containing flame retardant, (C) triazine skeleton-containing compound and (D) higher fatty acid amide compound, (A) is 50 to 80% by weight and (B) is 1
~ 45 wt% (C) is 1 to 30 wt%, (D) is 0 to 2
It is preferably in the range of 0% by weight. Outside the above range, the balance of volatility resistance, flame retardancy, impact resistance, heat resistance and fluidity tends to be lost.

The resin composition of the present invention can be obtained by, for example, melt-kneading the above-mentioned components in a commercially available single-screw extruder, a twin-screw extruder or the like. At that time, an antioxidant such as BHT, An ultraviolet 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 if necessary.

By subjecting the composition of the present invention thus obtained to, for example, injection molding or extrusion molding, a molded article excellent in 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, but the present invention is not limited thereto. The measurements in Examples and Comparative Examples were performed using the following methods or measuring instruments. (1) Weight average particle diameter of rubber: The weight average particle diameter of the rubber-modified styrene resin is calculated by the following formula by calculating the particle diameter of the butadiene polymer in the transmission electron microscope photograph taken by the ultrathin section method of the resin composition. Calculate 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 modification 18 g of methyl ethyl ketone on 1 g of styrene resin
Add a mixed solvent of milliliter and 2 milliliter of methanol, shake at 25 ℃ for 2 hours, 5 ℃, 18000 rpm
Centrifuge for 30 minutes at. The supernatant was taken out, the resin component was precipitated with methanol, and then dried.

0.1 g of the resin thus obtained was dissolved in toluene to give a solution having a concentration of 0.5 g / deciliter, 10 ml of this solution was placed in a Canon-Fenske viscometer, and the solution was allowed to flow at 30 ° C. The number of seconds t ₁ was measured. On the other hand, with the same viscometer, the flowing seconds of pure toluene t
₀ was measured and calculated by the following mathematical formula. 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 0 ° 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 according to ASTM-D256. (V notch, 1/8 inch test piece) (5) Vicat softening temperature; measured by a method according to ASTM-D1525 and used as a scale of heat resistance. (6) Melt flow rate (MFR): An index of fluidity, which was measured by a method according to ASTM-D-1238. It was determined from the extrusion amount (g / 10 min.) Per 10 minutes under the conditions of a load of 5 kg and a melting temperature of 200 ° C. (7) Flame retardancy and drip property VB (Vertical Bur) compliant with UL-94
(1/8 inch and 1/1)
Evaluation with 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) (manufactured by Nippon Zeon Co., Ltd., trade name Nipol 1220SL)]
Was dissolved in the following mixed solution to form a uniform solution.

Polybutadiene 10.5 wt% Styrene 74.2 〃 Ethylbenzene 15.0 〃 α-Methylstyrene dimer 0.27 〃 1,1-Bis (t-butylperoxy) -3,3,5-trimethyl Cyclohexane 0.03 〃 Then, the above mixture was continuously fed to a series four-stage reactor equipped with a stirrer, and the first stage had a stirring rate of 190 rpm, 126 rpm.
℃, the second stage is 50 rpm, 133 ℃, the third stage is 20 rp
m, 140 ° C, and the fourth stage was polymerized at 20 rpm and 155 ° C. Subsequently, the polymerization liquid having a solid content of 73% was introduced into a devolatilization device 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
%, 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 [Styron 680 (trade name: GPPS) manufactured by Asahi Kasei Corporation] was used. Manufacture of polyphenylene ether (PPE) After the inside of a stainless steel reactor having an oxygen blowing port at the bottom of the reactor and having a cooling coil and stirring blades inside was sufficiently replaced with nitrogen, cupric bromide 54.8 g , Di-n-
Butylamine 1110 g, and toluene 20 liters,
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 a reactor. Oxygen was continuously blown into the reactor while stirring, and polymerization was performed for 180 minutes while controlling the internal temperature at 30 ° C. After the polymerization was completed, the precipitated polymer was filtered off. A methanol / hydrochloric acid mixture was added to this to decompose the residual catalyst in the polymer, and the polymer was thoroughly washed with methanol and dried to obtain powdery polyphenylene ether (referred to as PPE). The reduced viscosity was 0.55 deciliter / g.

Further, this PPE and polystyrene (Styron 685, trade name, manufactured by Asahi Kasei Kogyo Co., Ltd.) in a weight ratio of 7
The mixture was mixed at 0/30 and melt-extruded at 350 ° C. in a twin-screw extruder. The obtained pellet is called PPE-MB. (B) Production of organic phosphorus compound (organic phosphorus compound containing hydroxyl group-containing aromatic phosphoric acid ester) Phenol 122.7 parts by weight (molar ratio 2.0), aluminum chloride 0.87 parts by weight (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 (molar ratio 1.0) of resorcin was added to the produced intermediate and further reacted. 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 the chlorine content, to obtain a phosphoric acid ester mixture (hereinafter referred to as FR). When this mixture was analyzed by GPC (gel permeation chromatography), diphenyl resorcinyl phosphate represented by the following formula 4 (hereinafter referred to as TPP-OH) and triphenyl phosphate represented by the following formula 12 (hereinafter referred to as TPP) were analyzed. ) And an aromatic condensed phosphoric acid ester (hereinafter referred to as TPP dimer)
And the weight ratio is 54.2 / 18.3 / 2, respectively.
It was 7.5.

[0048]

[Chemical formula 12]

[0049]

[Chemical 13]

(C) Compound containing triazine skeleton Melamine cyanurate commercially available as a compound containing triazine skeleton [trade name MC610 (manufactured by Nissan Kagaku KK)
)] Was used. In addition, the 10 wt% weight loss temperature of the MC was 351.8 ° C. (D) Higher fatty acid amide As a higher fatty acid amide, commercially available ethylene bis-stearyl amide {trade name Kao Wax EB FF manufactured by Kao Corporation
Was used (referred to as EBS)}. (E) Preparation and evaluation of composition The above HIPS-1 / GPPS / PPE-MB / FR / M
C / EBS in weight ratio 50/21/29/18/14 /
The mixture was mechanically mixed at a ratio of 2, and a Labo Plastomill manufactured by Toyo Seiki Seisakusho Co., Ltd. was used, and the melting temperature was 250 ° C. and the rotation speed was 50 rpm.
Melted for 5 minutes. A 1/8 inch thick test piece was prepared from the polymer composition thus obtained by hot pressing and evaluated for flame retardancy, volatile Vicat softening temperature, Izod impact strength and melt flow rate (MFR). I went. The results are shown in Table 1.

On the other hand, if the above resin composition is 30 mm
φ twin-screw extruder (Model AS3 manufactured by Nakatani Machinery Co., Ltd.)
0) was melt extruded at 260 ° C. to prepare pellets. Cylinder temperature of the pellets thus obtained was set to 230 by using an injection molding machine (model IS80A manufactured by Toshiba Machine Co., Ltd.).
C., the mold temperature was 20.degree. C., the injection time was 10 seconds, and the cooling time was 15 seconds, and 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 found on the mold surface.

[0052]

Example 2 (a) Production 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 (moles) The 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 was 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 reacted at 120 to 124 ° C. for 3 hours to precipitate crystals.

[0053]

[Chemical 14]

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

[0055]

[Chemical 15]

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

[0057]

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

[0058]

[Chemical 16]

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

[0060]

Example 4 (a) Triazine skeleton-containing compound (melon) As the triazine skeleton-containing compound, melon (Nissan Chemical Co., Ltd.) obtained by a thermal decomposition reaction of melamine was used. In addition, the weight loss temperature of the above melon is 522.1%.
It was ℃. (B) Preparation and Evaluation of Composition In Example 1, the same experiment as in Example 1 was repeated except that the above melon was used instead of MC. The results are shown in Table 1.

[0061]

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

[0062]

Comparative Example 2 (a) Triazine skeleton-containing compound (melamine) As the triazine skeleton-containing compound, commercially available melamine [manufactured by Mitsui Toatsu Chemicals, Inc. (referred to as ML)] was used. The 10% weight loss temperature of the melamine was 276.4 ° C. (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. The results are shown in Table 1. Further, as shown in Table 1, when melamine was used as the triazine skeleton-containing compound, many white powders adhered to the mold surface during injection molding.

[0063]

Example 5 The resin composition of Example 1 was treated with HIPS.
-1 / PPE-MB / FR / MC / EBS = 74/26
Example 19 except that the weight ratio is changed to / 19/15
The same experiment was repeated. The results are shown in Table 1.

[0064]

Example 6 The resin composition of Example 1 was treated with HIPS.
-1 / PPE-MB / FR / MC / EBS = 77/23
The same experiment as in Example 1 was repeated except that the weight ratio was changed to / 19/15/2. The results are shown in Table 1.

[0065]

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

[0066]

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

[0067]

[Example 9] (a) Rubber-modified styrenic resin In the production of HIPS-1 of Example 1, mineral oil (liquid paraffin) (Matsumura Oil Research Institute Co., Ltd., trade name Smoyl PS-260) was used as a resin component. The same polymerization as HIPS-1 was carried out except that 2% by weight was added therein.
(Referred to as HIPS-2) (b) Phosphorus-containing flame retardant As a phosphorus-containing flame retardant, red phosphorus powder [(Rin Kagaku Kogyo KK, trade name Nova Excel 150 (RP and (I.e.))) (C) Preparation and evaluation of the composition In Example 1, the resin composition was prepared according to the above 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). The results are shown in Table 1.

[0068]

[Table 1]

[0069]

The resin composition of the present invention is a resin composition excellent in low volatility, flame retardancy, good flowability, heat resistance and impact resistance. This composition is suitable for home electric appliance parts, OA equipment parts, and the like, and since it is particularly low in volatility, there is no deposit on the mold at the time of injection molding, and it plays a large role in these industries.

Claims (1)

[Claims] 1. A resin composition comprising (A) a thermoplastic resin, (B) an organic phosphorus compound and / or a phosphorus-containing flame retardant which is red phosphorus, and (C) a triazine skeleton-containing compound, C) A heating test in air, which is an index of the thermal decomposition temperature of the triazine skeleton-containing compound (heating rate: 10 ° C.)
/ Min), the temperature when reducing 10% by weight is 300
A low-volatile flame-retardant, heat-resistant and impact-resistant resin composition characterized by having a temperature of at least ℃.