JPH0711119A - Flame-retardant thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in processability, moldability, and material properties such as heat and impact resistances. CONSTITUTION:This resin composition comprises 40-90 pts.wt. aromatic polycarbonate resin (PC resin), 5-40 pts.wt. graft copolymer resin (ABS resin), and 1-30 pts.wt. aromatic diphosphate represented by the formula. It may optionally contain 0.1-1.0 pt.wt. PTFE. In the formula, R1, R2, R3, and R4 each independently is a 1-3C alkyl and Y is phenylene or biphenylene.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame-retardant thermoplastic resin composition. More specifically, an aromatic polycarbonate resin (hereinafter sometimes referred to as PC resin) and a graft copolymer resin (hereinafter sometimes referred to as ABS resin).
A base resin, a specific aromatic diphosphate as a flame retardant, and optionally polytetrafluoroethylene (hereinafter referred to as PTFE). The present invention relates to a resin composition.

[0002]

2. Description of the Related Art Conventionally, a resin mixture of PC resin and ABS resin has its own properties such as improved moldability of PC resin and improved impact resistance and heat resistance of ABS resin. The drawbacks are improved. Therefore, the resin material used is selected according to the physical properties required for the molded product. For example, automobile parts, household electric equipment parts, office equipment parts,
Since a resin material used for manufacturing mechanical parts and the like is required to have impact resistance and heat resistance, a mixture of PC resin and ABS resin is preferable. As these resin materials, it may be desired to further impart flame retardancy, and in this case, a flame retardant is blended, but regarding a resin composition containing a halogen-based flame retardant, for example, the present application The person is Japanese patent application 4-
We have already filed as No. 138080. However, the halogen-based flame retardant has a problem in use because it may be thermally decomposed when the resin composition is molded into a target product or may be converted into a harmful substance when the molded product becomes a waste.

For this reason, for example, phosphoric acid esters (phosphates) have come to be used as flame retardants other than halogen flame retardants. However, for example, a resin mixture of a PC resin and an ABS resin is blended with triphenyl phosphate (EP174493) or a phosphate-based oligomer which is a condensed phosphate ester (N
L8802346), but the phosphates used in these have low melting points and are in liquid form, resulting in poor compounding processability and inferior physical properties such as heat resistance. Has not been done.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above problems by incorporating a specific aromatic diphosphate and optionally PTFE in a resin mixture of a PC resin and an ABS resin, thereby solving the above problems. It is intended to provide a flame-retardant thermoplastic resin composition having excellent moldability and excellent physical properties such as heat resistance and impact resistance.

[0005]

That is, the gist of the present invention is (A) 40 to 90 parts by weight of an aromatic polycarbonate resin, and (B) a weight average rubber particle diameter of 0.15 to 0.35 μm.
A conjugated diene rubber polymer component which is m, a monomer component comprising an aromatic vinyl monomer, a vinyl cyanide monomer and a vinyl monomer copolymerizable with these, if necessary,
5 to 40 parts by weight of a graft copolymer resin consisting of, and (C) an aromatic diphosphate 1 represented by the following formula (I)
The flame-retardant thermoplastic resin composition is characterized by containing 30 to 30 parts by weight.

[Chemical 2] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent the same or different alkyl groups having 1 to 3 carbon atoms, and Y represents a phenylene group or a biphenylene group).

(A) Aromatic Polycarbonate Resin In the present invention, the aromatic polycarbonate resin is not particularly limited, and various kinds can be used. For example, a solvent method, that is, a so-called phosgene method in which a divalent phenol is reacted with a carbonate precursor such as phosgene in the presence of a known acid acceptor and a molecular weight modifier in a solvent such as methylene chloride, a divalent phenol and a diphenyl ether Aromatic polycarbonate resins obtained by a transesterification method of reacting with a carbonate precursor such as enyl carbonate are typical. Examples of the divalent phenol that can be preferably used include bisphenols, and 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “bis-phenol A”) is particularly preferable. Further, a part or all of bis-phenol A may be replaced with another divalent phenol. From the viewpoint of mechanical strength and moldability, the aromatic polycarbonate resin preferably has a viscosity average molecular weight of 10,000 to 100,000, and particularly preferably 15,000 to 40,000.

(B) Graft Copolymer Resin In the present invention, the graft copolymer resin means a conjugated diene rubber polymer component having a weight average rubber particle diameter of 0.15 to 0.35 μm and an aromatic vinyl. A graft copolymer resin composed of a monomer, a vinyl cyanide monomer, and optionally a monomer component composed of a vinyl monomer copolymerizable therewith. As the conjugated diene rubber polymer component constituting the graft copolymer resin, polybutadiene,
Examples thereof include a butadiene-styrene copolymer, a butadiene-acrylonitrile copolymer, polyisoprene and polychloroprene. The conjugated diene rubber polymer component may be one kind or a mixture of two or more kinds. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, dimethylstyrene, vinyltoluene and the like. Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile. Further, as vinyl monomers copolymerizable with these, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, maleimide, N-phenyl methacrylate. Examples thereof include enylmaleimide. These monomers may be one kind or a mixture of two or more kinds.

As the method for producing the graft copolymer resin of the present invention, known polymerization methods such as emulsion polymerization method, suspension polymerization method, bulk polymerization method, emulsion-suspension polymerization method and bulk-suspension polymerization method are used. Used in combination with batch and / or continuous mode.
In particular, an emulsion polymerization method is preferable among these production methods, and a rubber latex is used as the conjugated diene rubber polymer, and an aromatic vinyl monomer, a vinyl cyanide monomer and, if necessary, copolymerizable with them can be used. It is preferable to adopt a graft emulsion polymerization method in which a monomer mixture consisting of vinyl monomers is polymerized. By such a method, a monomer component composed of an aromatic vinyl monomer, a vinyl cyanide monomer and, if necessary, a vinyl monomer copolymerizable therewith, and a weight average rubber particle diameter of 0. It is possible to obtain the graft copolymer resin of the present invention comprising a conjugated diene rubber polymer component having a size of 15 to 0.35 μm. In the present invention, the weight average rubber particle diameter of the conjugated diene rubber polymer component dispersed in the graft copolymer resin is 0.15.
.About.0.35 .mu.m is required. When the weight average rubber particle diameter is 0.15 μm or less, the impact resistance of the finally obtained resin composition is remarkably inferior.
If it is larger than 35 μm, flame retardancy such as drip property of the resin composition finally obtained may not be satisfied, which is not preferable.

Further, such 0.15 to 0.35 μm
The rubber latex of the conjugated diene polymer having a weight average rubber particle diameter of 1 may be obtained by performing an operation of particle diameter enlargement in order to obtain target rubber particles from a rubber latex having a small particle diameter of 0.15 μm or less. Particle size enlargement is a known method,
For example, a method of freezing rubber latex once and then re-dissolving it, adding mineral acid, organic acid, etc. to rubber latex,
A method of temporarily lowering the pH of the rubber latex, a method of applying a shearing force to the rubber latex, etc. (JP-A-54-13)
3588, JP-A-59-202121). In particular, the method of adding phosphoric acid or acetic anhydride to the rubber latex is preferable because the particle size can be easily adjusted. The distribution of the rubber particle diameter of the conjugated diene rubber polymer does not necessarily have to be monomodal, and may be multimodal, that is, may be obtained by mixing rubbers having different rubber particle diameters. In the present invention, the weight average rubber particle size of the conjugated diene rubber polymer component means Coulter Electronics Lt.
With the "Coulter Nano-Sizer ^™ " manufactured by d.), the latex of the raw rubber before graft polymerization can be expressed by the weight average rubber particle diameter measured in a system in which water is dispersed at 23 ° C.

The composition ratio of the conjugated diene rubber polymer component and the monomer component in the graft copolymer resin is such that the conjugated diene rubber polymer component is 10 to 70% by weight and the monomer component 90.
The range of ˜30 wt% is preferred. More preferably, the conjugated diene rubber polymer component is in the range of 45 to 70% by weight, and the monomer component is in the range of 55 to 30% by weight. By adopting this range, the flame retardancy is easily improved. Further, the composition ratio of the aromatic vinyl monomer, the vinyl cyanide monomer, and the vinyl monomer copolymerizable therewith in the monomer component is 40 to 80% by weight of the aromatic vinyl monomer. %, 1 to 40% by weight of vinyl cyanide monomer, and 0 to 59% by weight of vinyl monomer copolymerizable therewith. Outside of this range, the physical properties of the graft copolymer resin, such as heat resistance and miscibility with other resins, may change, resulting in poor physical properties of the flame-retardant thermoplastic resin composition obtained.

Specific examples of the graft copolymer resin of the present invention include ABS resins such as acrylonitrile / butadiene / styrene copolymer and methyl methacrylate / acrylonitrile / butadiene / styrene copolymer. By blending this graft copolymer resin with other resin composition raw materials, the resulting resin composition can exhibit excellent physical property balance, flame retardancy, and moldability.

(C) Aromatic Diphosphate The aromatic diphosphate represented by the above formula (I) used in the present invention is an orthophosphoric acid ester of a dialkylphenol and a dihydroxyaromatic compound. When this aromatic diphosphate is added to the resin composition of the present invention, it acts as a flame retardant with which a good flame retardant effect can be obtained, and is miscible with the resin composition of the present invention, heat resistance, low volatility, moldability, Provides excellent physical properties such as impact resistance. This aromatic diphosphate is, for example, (2,6-xylyl) phosphochloridate obtained by reacting 2,6-xylenol with phosphorus oxychloride in the presence of a Lewis acid catalyst, and further in the presence of a Lewis acid catalyst, resylcin, hydroquinone or It can be obtained by reacting a dihydroxy aromatic compound such as 4,4′-bisphenol. The aromatic diphosphate in the present invention is represented by the formula (I):
R ₁ , R ₂ , R ₃ and R ₄ are methyl groups and Y is m
-Or p-phenylene group, or 3,3'-, 3,
Those having a 4'- or 4,4'-biphenylene group are preferred. More preferably, tetra (2,6-xylyl) resorcin diphosphate, tetra (2,6-xylyl) hydroquinone diphosphate, and tetra (2,6-xylyl) 4,4'-bisphenol diphosphate are Can be mentioned. These may be one kind or a mixture of two or more kinds. If the aromatic diphosphate is out of the constitutional range of the present invention, the heat resistance is low, the volatility and the plate-out property are high, and the physical properties of the resin composition of the present invention are deteriorated, which is not preferable.

(D) Polytetrafluoroethylene In the present invention, in addition to the above components (A) to (C),
Polytetrafluoroethylene can be included. This polytetrafluoroethylene is a fluorocarbon polymer obtained by polymerizing tetrafluoroethylene as a main component, and is abbreviated as PTFE. By incorporating PTFE into the resin composition, the flame retardancy of the resin composition, particularly the drip property, can be improved.

The content ratio of each component constituting the resin composition of the present invention is (A) PC resin 40 to 90 parts by weight, (B) A
5 to 40 parts by weight of BS resin, 1 to 30 parts by weight of (C) aromatic diphosphate, and optionally (D) PTFE0.
1 to 1.0 parts by weight (however, the total of each component is 10
0 parts by weight. ). If the content is out of the above range, the physical properties of the resulting resin composition such as mechanical strength and workability are deteriorated.

In the method for producing the resin composition of the present invention, first, the PC resin, ABS resin, aromatic diphosphate, and optionally PTFE, as described above, are weighed and mixed. The obtained blended compound may be a dry blend as it is, but more preferably it is subjected to a melt-kneading step and melt-mixed. In order to mix the components of the resin composition of the present invention, and to mix and knead them, known mixing and kneading methods may be used. For example, one or a mixture of two or more of these constituents of the present invention in the form of powder, beads, flakes or pellets is added to an extruder such as a single screw extruder or a twin screw extruder, or a Banbury mixer, a pressure kneader, The resin composition can be further melt-mixed with a processing device such as a kneader such as a two-roll mill.

Further, the resin composition according to the present invention includes other resins and lubricants, mold release agents, colorants, antistatic agents, in types and amounts that do not impair the properties of the resin composition of the present invention,
Various resin additives such as other flame retardants, ultraviolet absorbers, light resistance stabilizers, heat resistance stabilizers and fillers can be added in an appropriate combination. Other resins that can be added include AS resin, MBS resin, AAS resin, AES resin, ACS resin, PA resin, PBT resin,
Examples thereof include PET resins, and particularly preferred are aromatic vinyl monomer components 60 to 80% by weight, vinyl cyanide monomer components 1 to 40% by weight, and vinyl monomer components copolymerizable therewith. It is an AS resin (E) which is a copolymer composed of 0 to 39% by weight (however, the total amount of the monomer components is 100% by weight), and is 0 to 30 parts by weight in the resin composition of the present invention. It is possible to substitute and blend a part of the ABS resin (B). Also, as the filler,
Glass fiber, metal fiber, carbon fiber, fibrous reinforcing agent such as potassium titanate whiskers, talc, clay, calcium carbonate, mica, glass flake, milled fiber, metal flake, metal powder and the like can be mentioned, and these can be used alone. However, it is also possible to combine two or more kinds in combination.

[0017]

The present invention is as described above,
It has a particularly remarkable effect as follows, and its industrial utility value is extremely large. (1) The resin composition according to the present invention is a PC resin, ABS.
A flame retardant comprising a resin and a specific aromatic diphosphate, and optionally PTFE, can be used as a flame retardant thermoplastic resin material having extremely excellent moldability and physical properties. (2) Since the resin composition according to the present invention is prepared by optimizing and blending the respective components, the resin composition exhibits excellent heat resistance and excellent fluidity, which are the characteristics of each resin, and the molding process is performed. It is possible to shorten the cycle. (3) The resin composition according to the present invention is formed into a molded article by various processing methods such as injection molding method, extrusion molding method and thermoforming method, and has excellent flame retardancy, processability, heat resistance and impact resistance. It can be used for required applications, for example, electric parts such as office equipment and household electric equipment, and industrial parts such as automobiles and ships.

[0018]

EXAMPLES The following examples and comparative examples serve to explain the present invention more specifically. The present invention is not limited to the following examples as long as the gist thereof is not exceeded. In addition, "part", "%", and ratio are based on weight.

In each of the following examples and comparative examples, the physical properties of the flame-retardant thermoplastic resin composition were measured by the following methods. (1) Flexural modulus (kg / cm ² ) Measured in accordance with JIS K7113. (2) Izod impact strength (with notch) (kg · cm / cm) Measured according to JIS K7110. (3) Heat resistance (° C.) Measured in accordance with ASTM D3769. (1 mm deformation temperature by heat sag test method) (2 mmt, 100 mm overhang) (4) Spiral flow length (cm) Regarding fluidity, a spiral mold with a thickness of 2 mm and a width of 8 mm is manufactured by Nissei Plastic Industry Co., Ltd. Injection was carried out using a FS80 type injection molding machine at a resin temperature of 240 ° C., an injection pressure of 910 kg / cm ² , and a mold temperature of 60 ° C., and the spiral flow length was measured. (5) Plate-out property Regarding the plate-out property, using a Hishiya Seiko VP40 injection molding machine, the resin and fat temperature was 260 ° C and the injection pressure was 900.
Molding was carried out for 1000 shots at kg / cm ² and a mold temperature of 60 ° C. After the completion of molding, the mold surface was observed to confirm the presence or absence of deposits. (6) Flame retardance Based on Subject 94 (UL94) standardized by US Underwriters Laboratories (UL)
A 1.6 mm thick combustion test was conducted and classified into V-0 and V-1 flame-retardant classes: ◎ (V-0 pass), ○ (V-1 pass), X (V-0, V -1 was rejected). Drip: In a flammability test, it was determined whether flammable drops ignite dry surgical cotton wool 12 inches (305 mm) below the sample.

Production Example (B) Production of Graft Copolymer Resin

B-1 A reactor having a capacity of 5 L equipped with a stirrer, a heating and cooling device, and each raw material and an auxiliary charging device was charged with polybutadiene rubber latex as a conjugated diene rubber polymer and acetic anhydride (A).
100 parts of 0.25 μm particle-size-enlarged solids using A) and 270 parts of deionized water (including water in the latex) were charged, and the temperature was raised to 70 ° C. 60
Sodium pyrophosphate 1.0 dissolved in 45 parts of water at ℃
Parts, dextrose 0.5 parts and ferrous sulfate 0.01
Parts were added. 70 hours of styrene, 30 parts of acrylonitrile, and 1.1 parts of t-dodecyl mercaptan while maintaining the temperature at 70 ° C. for 2 hours and 30 minutes from the time when the temperature reached 70 ° C.
And cumene hydroperoxide 0.5 part, disproportionated potassium rosinate soap 1.8 parts, potassium hydroxide 0.3
7 parts, 35 parts deionized water were added. After the addition was completed, the reaction was continued for another 30 minutes and cooled to complete the reaction. The results are shown in Table-1. After adding 5 parts of an anti-aging agent to this graft copolymer latex, it is added to an aqueous solution of magnesium sulfate heated to 95 ° C with stirring to coagulate, and the coagulated product is washed with water and dried to give a white powdered graft copolymer resin. (B
-1) was obtained.

B-2 In the same reactor as in (B-1), polybutadiene rubber latex as a conjugated diene rubber polymer was used and its particle size was enlarged to 0.30 μm using acetic anhydride to obtain a solid content of 100.
And 270 parts of deionized water (including water in the latex) were charged, and the temperature was raised to 70 ° C. At 4 ° C, water 4
0.82 parts of sodium pyrophosphate, 0.4 parts of dextrose and 0.008 parts of ferrous sulfate dissolved in 5 parts were added. It takes 2 hours and 15 minutes from when the temperature reaches 70 ° C.
While maintaining the temperature at 70 ° C, 57.3 parts of styrene, 24.5 parts of acrylonitrile, and 0.9 t-dodecyl mercaptan.
Parts, cumene hydroperoxide 0.4 parts, disproportionated potassium rosinate soap 1.5 parts, potassium hydroxide 0.3 parts, deionized water 30 parts were added. After the addition is complete
The reaction was continued for another 15 minutes, cooled, and terminated. After adding 5 parts of an anti-aging agent to this graft copolymer latex, it is added to an aqueous solution of magnesium sulfate heated to 95 ° C with stirring to coagulate, and the coagulated product is washed with water and dried to give a white powdered graft copolymer resin. (B-2) was obtained.

B-3 Except that phosphoric acid (PA) was used to increase the particle size of polybutadiene rubber latex as the conjugated diene rubber polymer, (B-
1) and the graft copolymer resin (B-
3) was obtained.

In the same reactor as B-4 (B-1), polybutadiene rubber latex as a conjugated diene rubber polymer was used, and the particle size was enlarged to 0.25 μm using acetic anhydride.
And 300 parts of deionized water (including water in the latex) were charged, and the temperature was raised to 80 ° C. Upon reaching 80 ° C., potassium persulfate dissolved in 6 parts of deionized water.
2 parts and 0.45 part of disproportionated potassium rosinate soap were added, and while maintaining at 80 ° C. for 2 hours and 45 minutes from this point, 70 parts of styrene, 30 parts of acrylonitrile, t-
0.3 parts of dodecyl mercaptan were added. 30 minutes after the start of addition, 0.6 part of potassium persulfate, 1.35 parts of disproportionated potassium rosinate soap, 0.2 parts of potassium hydroxide
5 parts and 40 parts deionized water were added over 2 hours and 15 minutes. After the addition was completed, the reaction was continued for another 30 minutes and cooled to complete the reaction. After adding 5 parts of an anti-aging agent to this graft copolymer latex, it is added to an aqueous solution of magnesium sulfate heated to 95 ° C with stirring to coagulate, and the coagulated product is washed with water and dried to give a white powdered graft copolymer resin. (B-4) was obtained.

B-5 Polybutadiene rubber latex as a conjugated diene rubber polymer was enlarged in particle size to 0.30 and 0.65 μm by using acetic anhydride, and 70 parts and 30 parts as solid contents were used in combination, respectively. The same procedure as in (B-1) was carried out except that a rubber latex adjusted to have an average rubber particle diameter of 0.40 μm was charged, and a white powdery graft copolymer resin (B-
5) was obtained.

In the same reactor as B-6 (B-1), polybutadiene rubber latex as a conjugated diene rubber polymer was used as acetic anhydride to increase the particle size to 0.30 and 0.65 μm, respectively, to obtain solids. 70 parts and 30 parts were used together, and rubber latex which was adjusted to have a weight average rubber particle diameter of 0.40 μm, and 300 parts of deionized water (including water in the latex) were charged, and the temperature was raised to 80 ° C. did. When the temperature reached 80 ° C, 0.3 parts of potassium persulfate dissolved in 6 parts of deionized water.
Part, 0.65 parts of disproportionated potassium rosinate soap are added,
From this point, 105 parts of styrene, 45 parts of acrylonitrile and 0.45 part of t-dodecyl mercaptan were added over 4 hours while maintaining the temperature of the polymerization reactor at 80 ° C.
45 minutes after the start of addition, potassium persulfate 0.9
Parts, 2.0 parts of disproportionated potassium rosinate soap, 0.35 parts of potassium hydroxide, and 40 parts of deionized water were added over 3 hours and 15 minutes. After the addition is complete, continue the reaction for another 30 minutes,
The reaction was completed by cooling. The results are shown in Table-1. After adding 5 parts of an anti-aging agent to this graft copolymer latex, it is added to an aqueous solution of magnesium sulfate heated to 95 ° C with stirring to coagulate, and the coagulated product is washed with water and dried to give a white powdered graft copolymer resin. (B-6) was obtained.

[0027]

[Table 1] Table-1 ──────────────────────────────────── Graft copolymer resin (B ) B-1 B-2 B-3 ──────────────────────────────────── Weight average rubber particles Diameter (μm) 0.25 0.30 0.25 Polybutadiene content% 50 50 55 50 Polymerization initiator Redox type Redox type Redox type Particle size enlargement adjuster A A A A A A PA PA ────────────── ───────────────────────

[Table 2] Table-1 (continued) ──────────────────────────────────── Graft copolymer Resin (B) B-4 B-5 B-6 ──────────────────────────────────── Weight Average rubber particle diameter (μm) 0.25 0.40 0.40 Polybutadiene content% 50 50 40 Polymerization initiator KSO-based redox-based KSO-based particle size enlargement regulator AA AA AA ──────────── ──────────────────────────

(C) Aromatic Phosphate C-1 Tetra (2,6-xylyl) resorcinic diphosphate (shown by formula (II). PX200, glass transition temperature 96)
℃, manufactured by Daihachi Chemical Co., Ltd.)

[Chemical 3]

C-2 Tetra (2,6-xylyl) hydroquinone diphosphate (shown by formula (III). PX201, glass transition temperature 16)
9 ° C, manufactured by Daihachi Chemical Co., Ltd.)

[Chemical 4]

C-3 Tetra (2,6-xylyl) 4,4'-bisphenol diphosphate (represented by formula (IV): PX202, glass transition temperature 182 ° C., manufactured by Daihachi Chemical Co., Ltd.)

[Chemical 5]

C-4 triphenyl phosphate (shown by formula (V). TPP,
(Melting point 49 ° C)

[Chemical 6]

C-5 Aromatic phosphate-based oligomer (shown by the formula (VI). CR
733S, melting point unknown: liquid at 23 ° C, Daihachi Chemical Co., Ltd.
Made)

[Chemical 7] (However, n is an integer of 1 or more)

Examples 1 to 9 and Comparative Examples 1 to 6 PC resin (A) (NOVAREX ^™ 7022A, viscosity average molecular weight 21,000, manufactured by Mitsubishi Kasei Co., Ltd.), obtained by the method described in the above Production Example. Graft copolymer resin (AB
S resin) (B), aromatic phosphate (the above formula (II) to
(VI)) (C) and, if necessary, PTFE (D)
(Polyflon ^™ F201, manufactured by Daikin Co., Ltd.), AS resin (E) (composition ratio: styrene / acrylonitrile = 70
/ 30, molecular weight 120,000), the respective components were weighed at the blending ratio (parts) shown in Table 2, and mixed by a tumbler, and the obtained mixture was mixed with a vented twin-screw extruder to remove volatile components. Melting and kneading were carried out while removing the pellets of the resin composition. From the pellets of the obtained resin composition, various physical property test pieces were prepared by an injection molding machine and used for the test. The results are shown in Table-2-1 to Table-2-5.

[0034]

[Table 3] Table 2-1 ──────────────────────────────────── Example 1 2 3 ──────────────────────────────────── Mixing ratio PC (A) 60 77 50 ABS (B) ( B-4) (B-4) (B-4) 18 9 22 C-1 0 0 0 C-2 12.8 9.3 16.8 C-3 0 0 0 PTFE (D) 0.2 0. 2 0.2 AS (E) 9 4.5 11 ───────────────────────────────────── Difficulty Flammability UL94 ◎ ◎ ◎ Maximum burning time (sec) 4 3 7 Total burning time (sec) 23 16 26 Drip None None None None ─────────────────────── ────────────── Physical properties Flexural modulus 25000 5700 24300 Izod impact strength 64 64 61 Heat resistance 100 105 105 Spiral flow length 40 35 45 Plate out property None None None ──────────────────────── ─────────────

[0035]

[Table 4] Table-2-2 ──────────────────────────────────── Example 4 5 6 ──────────────────────────────────── Blending ratio PC (A) 60 60 60 60 ABS (B) ( B-4) (B-4) (B-1) 18 18 18 C-1 12.8 0 0 C-2 0 0 12.8 C-3 0 12.8 0 PTFE (D) 0.2 0. 2 0.2 AS (E) 9 9 9 ──────────────────────────────────── Flame retardant UL94 ◎ ◎ ◎ Maximum burning time (sec) 3 9 6 Total burning time (sec) 18 31 25 Drip None None None None ───────────────────────── ──────────── Physical properties Flexural modulus 25200 2 400 25 100 Izod impact strength 61 62 62 Heat resistance 88 94 100 Spiral flow length 42 38 40 Plate-out property None None None ──────────────────────── ─────────────

[0036]

[Table 5] Table-2-3 ──────────────────────────────────── Example 7 89 ──────────────────────────────────── Mixing ratio PC (A) 60 60 50 ABS (B) ( B-2) (B-3) (B-1) 16.4 18 22 C-1 0 0 0 C-2 12.8 12.8 16.8 C-3 0 0 0 PTFE (D) 0.2 0.2 0.2 AS (E) 10.6 9 11 ──────────────────────────────────── ─ Flame retardancy UL94 ◎ ◎ ○ Maximum burning time (sec) 7 6 16 Total burning time (sec) 29 24 76 No drip None None None ───────────────────── ──────────────── Physical properties Flexural modulus 24200 25200 24400 Izod impact strength 75 65 59 59 Heat resistance 100 100 94 Spiral flow length 39 41 42 Plate-out property None None None None ────────────────────── ──────────────

[0037]

[Table 6] Table-2-4 ──────────────────────────────────── Comparative Example 1 2 3 ──────────────────────────────────── Blending ratio PC (A) 60 60 60 60 ABS (B) ( B-6) (B-4) (B-4) 22.5 18 18 C-2 12.8 0 0 C-4 0 12.8 0 C-5 0 0 12.8 PTFE (D) 0.2 0.2 0.2 AS (E) 4.5 9 9 ──────────────────────────────────── ─ Flame retardant UL94 × ◎ ◎ Maximum burning time (seconds) 10 8 4 Total burning time (seconds) 35 26 21 Dripping Yes No No ───────────────────── ──────────────── Physical properties Flexural modulus 24 00 26900 26100 Izod impact strength 73 58 71 Heat resistance 100 70 80 Spiral flow length 40 47 45 Plate-out property No Yes No None ─────────────────────── ──────────────

[0038]

[Table 7] Table-2-5 ──────────────────────────────────── Comparative Example 4 5 6 ──────────────────────────────────── Blending ratio PC (A) 35 95 60 ABS (B) ( B-4) (B-4) (B-5) 28 2 18 C-2 22.8 2.8 12.8 C-4 0 0 0 C-5 0 0 0 PTFE (D) 0.2 0. 2 0.2 AS (E) 140 9 ──────────────────────────────────── Flame retardant UL94 × × × Maximum burning time (sec) ＞ 60 15 9 Total burning time (sec) ＞ 250 55 35 Dripping Yes Yes Yes ──────────────────────── ────────────── Physical properties Flexural modulus 2380 0 24000 25300 Izod impact strength 35 27 66 Heat resistance 90 110 100 Spiral flow length 44 27 40 Plate out property None None None None ─────────────────────── ──────────────

From (Table-2), the following is clarified. (1) Since the resin composition according to the present invention uses the graft copolymer resin (B) prepared so as to be compatible with other mixed resin compositions, it has excellent moldability and physical properties. It can be used as a flame-retardant thermoplastic resin material. (2) In the resin composition according to the present invention, each resin is optimized and blended, so that the resin composition exhibits excellent heat resistance and excellent fluidity, which are the characteristics of each resin, and the molding process is performed. It is possible to shorten the cycle. (Example 1
~ 9). On the other hand, if it deviates from this range, the flame retardance standard cannot be satisfied (Comparative Examples 1, 4 to 6), the continuous moldability is poor (plate-out) (Comparative Example 2), the heat resistance is low and the molding process is performed. Only the product with a difficult cycle reduction (Comparative Example 3) can be obtained.

Claims (2)

[Claims] 1. An (A) aromatic polycarbonate resin 40-
90 parts by weight, (B) a conjugated diene rubber polymer component having a weight average rubber particle diameter of 0.15 to 0.35 μm, an aromatic vinyl monomer, a vinyl cyanide monomer and, if necessary, these 5 to 40 parts by weight of a graft copolymer resin composed of a monomer component composed of a vinyl monomer copolymerizable with, and (C) an aromatic diphosphate 1 represented by the following formula (I)
The flame-retardant thermoplastic resin composition is characterized by containing 30 to 30 parts by weight. [Chemical 1] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent the same or different alkyl groups having 1 to 3 carbon atoms, and Y represents a phenylene group or a biphenylene group.) 2. (A) Aromatic polycarbonate resin 40 to
90 parts by weight, (B) a conjugated diene rubber polymer component having a weight average rubber particle diameter of 0.15 to 0.35 μm, an aromatic vinyl monomer, a vinyl cyanide monomer and, if necessary, these 5 to 40 parts by weight of a graft copolymer resin consisting of a monomer component composed of a vinyl monomer copolymerizable with (C) an aromatic diphosphate 1 represented by the formula (I) according to claim 1. To 30 parts by weight, and (D) 0.1 to 1.0 parts by weight of polytetrafluoroethylene, a flame-retardant thermoplastic resin composition.