JP2001106860A - Flame retardant thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame retardant thermoplastic resin composition which excels in transparency, flame retardance, and heat resistance and substantially has transparency. SOLUTION: This flame retardant thermoplastic resin composition having excellent transparency, flame retardance, and heat resistance can be produced by combinedly using a specific bromine based flame retardant and a phosphoric ester compound in a thermoplastic resin comprising (A) a graft copolymer obtained by grafting a vinyl type monomer onto a rubbery polymer and (B) a vinyl type (co)polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant thermoplastic resin composition having excellent flame retardancy and heat resistance.

[0002]

2. Description of the Related Art A transparent polymer obtained by graft copolymerization of a vinyl polymer such as vinyl cyanide such as acrylonitrile or methacrylonitrile or an aromatic vinyl such as styrene or α-methylstyrene onto a rubbery polymer such as a diene rubber. Thermoplastic resin composition having impact resistance, moldability, appearance,
It is excellent in transparency and the like, and is widely used for applications such as OA equipment, home appliances, and general goods.

However, most plastics are flammable, and various techniques have been devised for flame retardancy due to safety issues.

[0004] In general, a method of blending a chlorine and bromine-based flame retardant having high flame retardancy with antimony oxide in a resin to make the resin flame retardant is adopted.

[0005] However, when applied to a thermoplastic resin having transparency, transparency has been lost, coloring is remarkable even if it is transparent, and a resin having both transparency and flame retardancy has not been obtained.

As a technique for imparting flame retardancy while maintaining transparency, for example, Japanese Patent Application Laid-Open No. Sho 62-116648 proposes the use of tetrabromobisphenol A as a flame retardant. Flame retardants have low heat resistance and have problems such as gas generation during molding. Japanese Unexamined Patent Publication (Kokai) No. 4-325564 proposes a brominated aromatic triazine-based flame retardant as a flame retardant. However, it is necessary to use antimony trioxide in combination, and thus, transparency cannot be maintained. Was. Further, as disclosed in Japanese Patent Application Laid-Open No. 8-277344, a method of adding a phosphorus compound to a resin has been proposed, but the flame retardancy was not sufficient.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a substantially transparent flame-retardant thermoplastic resin composition which overcomes the above-mentioned disadvantages of the prior art and has excellent flame retardancy and heat resistance. To provide.

[0008]

According to the present invention, an aromatic vinyl monomer (b), a vinyl cyanide monomer (c), an unsaturated alkyl carboxylate, A graft copolymer (A) obtained by graft copolymerizing at least one monomer selected from an ester monomer (d) and another copolymerizable vinyl monomer (e); Aromatic vinyl monomer (b), vinyl cyanide monomer (c),
A vinyl polymer (B) comprising one or more monomers selected from unsaturated carboxylic acid alkyl ester monomers (d) and other copolymerizable vinyl monomers (e); Of a brominated aromatic triazine-based flame retardant (II) and 2 to 30 parts by weight of a phosphate ester compound (III) 1 to 100 parts by weight of a thermoplastic resin (I) containing 10:90 to 60:40 by weight. 30 parts by weight and the weight ratio ｛(II) / (II
I) A flame-retardant thermoplastic resin composition added so that｝ is 1 or more.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The rubbery polymer (a) used for the graft copolymer (A) in the present invention is not particularly limited, but diene rubber, acrylic rubber, ethylene rubber and the like can be used. Specific examples include polybutadiene, poly (butadiene-styrene), poly (butadiene-acrylonitrile), polyisoprene, poly (butadiene-butyl acrylate), poly (butadiene-methyl methacrylate), and poly (butyl acrylate-methyl methacrylate). ), Poly (butadiene-ethyl acrylate), ethylene-propylene rubber, ethylene-propylene-diene rubber, poly (ethylene-isoprene), poly (ethylene-methyl acrylate) and the like. These rubbery polymers (a) are used alone or in a mixture of two or more. Among these rubbery polymers (a), polybutadiene, poly (butadiene-styrene), poly (butadiene-acrylonitrile) and ethylene-propylene rubber are preferably used in view of impact resistance.

The weight average particle diameter of the rubbery polymer (a) constituting the graft copolymer (A) in the present invention is not particularly limited, but is preferably 0.1 to 0.5 μm. 0.1μ
When the particle size is less than m, the impact strength of the obtained thermoplastic composition decreases, which is not preferable. When the particle size exceeds 0.5 μm, the transparency often decreases. More preferably 0.15-
0.4 μm.

The aromatic vinyl monomer (b) used in the graft copolymer (A) and the vinyl (co) polymer (B) in the present invention is not particularly limited. -Methylstyrene, orthomethylstyrene, paramethylstyrene, para-t-butylstyrene, halogenated styrene and the like, and one or more of them can be used. Of these, styrene and α-methylstyrene are preferred, and styrene is particularly preferred.

The vinyl cyanide monomer (c) used for the graft copolymer (A) and the vinyl (co) polymer (B) in the present invention is not particularly limited, but specific examples include acrylonitrile and methacrylic acid. Lonitrile and the like,
One or more kinds can be used. Among them, acrylonitrile is preferred in terms of impact resistance.

The unsaturated carboxylic acid alkyl ester monomer (d) used for the graft copolymer (A) and the vinyl (co) polymer (B) in the present invention is not particularly limited, but has 1 to 4 carbon atoms. Acrylic esters and / or methacrylic esters having 6 alkyl groups or substituted alkyl groups are suitable, and one or more kinds can be used. Specific examples include methyl (meth) acrylate,
Ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate,
Examples thereof include cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate and 2-chloroethyl (meth) acrylate, with methyl methacrylate being preferred.

The other copolymerizable vinyl monomer (e) used for the graft copolymer (A) and the vinyl (co) polymer (B) in the present invention is not particularly limited. , Maleimide compounds such as N-methylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide; unsaturated dicarboxylic acids such as maleic acid; unsaturated dicarboxylic anhydrides such as maleic anhydride; and unsaturated amide compounds such as acrylamide. And a copolymerizable vinyl compound.
More than one species can be used.

The vinyl (co) polymer (B) may be of a plurality of types.

The difference in the refractive index between the rubbery polymer (a) and the matrix resin is preferably 0.03 or less. The matrix resin referred to here comprises a graft copolymer component and a vinyl (co) polymer (B) obtained by removing the rubbery polymer (a) from the graft copolymer (A). The refractive indexes of the rubbery polymer (a), the graft copolymer component and the vinyl (co) polymer (B) are measured using an Abbe refractometer. The difference between the refractive indices of the rubbery polymer (a), the graft copolymer component and the vinyl (co) polymer (B) is 0.
When it exceeds 03, the transparency is reduced.

The brominated aromatic triazine flame retardant (II) of the present invention is not particularly limited, but has a melting point of 200.
To 250 ° C, more preferably 210 to 240 ° C. Further, those exhibiting a characteristic in which a 10% weight loss point according to a heat weight loss curve is 300 ° C. or more are preferable.

Preferred specific examples of the brominated aromatic triazine flame retardant (II) of the present invention are 2,4,6-tris (2,2)
4,6-tribromophenoxy) -1,3,5-triazine, 2,4,6-tris (1,3-dibromophenoxy) -1,3,5-triazine, 2,4,6-tris (mono Bromophenoxy) -1,3,5-triazine, the most preferred compound being 2,4,6-tris (2,
4,6-tribromophenoxy) -1,3,5-triazine.

As a preferred method of synthesizing 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine, for example, an aqueous solution of tribromophenolate is added with a phase transfer catalyst. Was added to the solution of the cyanuric chloride non-hydrophilic solvent at a temperature not higher than the boiling point of the solvent used, and further subjected to an aging reaction for 1 to 5 hours at a temperature lower than the boiling point of the solvent composition of the reaction system. It is obtained by removing the solvent from the reaction system.

The amount of the brominated aromatic triazine-based flame retardant (II) of the present invention is 2 to 30 parts by weight based on 100 parts by weight of the thermoplastic resin (I). When the amount of the brominated aromatic triazine-based flame retardant is less than 2 parts by weight, no flame retardancy is exhibited, and when it exceeds 30 parts by weight, impact resistance and thermal stability are remarkably poor.

The phosphoric ester compound (III) of the present invention is not particularly limited. For example, those represented by the following general formula (*), other condensed phosphoric ester,
Halogen-containing phosphoric acid esters or halogen-containing condensed phosphoric acid esters are preferred because they have a good balance of flame retardancy and heat resistance.

[0022]

Embedded image

In the formula (*), X is an arylene group, R 1, R
2, R3 and R4 each represent a substituted or unsubstituted phenyl group.

Examples of the arylene group include an o-phenylene group, an m-phenylene group, a p-phenylene group, a biphenylene group and a phenyleneoxyphenylene group.
Among them, an m-phenylene group and a p-phenylene group are preferably used.

R 1, R 2, R 3, R 4 are substituted or unsubstituted phenyl groups, but “R 1, R 2, R 3, R
4, at least one of which is an alkyl-substituted phenyl group having 1 to 6 carbon atoms ", and furthermore," R1, R2, R3, R4
Is preferably an alkyl-substituted phenyl group having 1 to 6 carbon atoms ", and further, a structure wherein" R1, R2, R3, and R4 are disubstituted phenyl groups having 1 to 6 carbon atoms "is preferably used. Further, the number of carbon atoms of the alkyl group is 1 to 3
Is preferably used.

As a specific example represented by the formula (*),
4-phenylene-tetrakis (2,6-dimethylphenyl) phosphate, 1,4-phenylene-tetrakis (3,5-dimethylphenyl) phosphate, 1,4
-Phenylene-tetrakis (2,6-diethylphenyl) phosphate, 1,4-phenylene-tetrakis (3,5-diethylphenyl) phosphate, 1,4
-Phenylene-tetrakis (2,6-dipropylphenyl) phosphate, 1,4-phenylene-tetrakis (3,5-dipropylphenyl) phosphate, 1,
3-phenylene-tetrakis (2,6-dimethylphenyl) phosphate, 1,3-phenylene-tetrakis (3,5-dimethylphenyl) phosphate, 1,3
-Phenylene-tetrakis (2,6-diethylphenyl) phosphate, 1,3-phenylene-tetrakis (3,5-diethylphenyl) phosphate, 1,3
-Phenylene-tetrakis (2,6-dipropylphenyl) phosphate, 1,3-phenylene-tetrakis (3,5-dipropylphenyl) phosphate, 4,
4'-biphenylene-tetrakis (2,6-dimethylphenyl) phosphate, 4,4'-biphenylene-tetrakis (3,5-dimethylphenyl) phosphate, 4,4'-biphenylene-tetrakis (2,6 -Diethylphenyl) phosphate, 4,4'-biphenylene-tetrakis (3,5-diethylphenyl) phosphate, 4,4'-biphenylene-tetrakis (2,
6-dipropylphenyl) phosphate, 4,4′-
Biphenylene-tetrakis (3,5-dipropylphenyl) phosphate, 1,4-phenylene-tetrakis (2-methylphenyl) phosphate, 1,4-phenylene-tetrakis (3-methylphenyl) phosphate, 1,4-phenylene-tetrakis (4-methylphenyl) phosphate, 1,4-phenylene-tetrakis (5-methylphenyl) phosphate, 1,4-phenylene-tetrakis (4-methylphenyl) phosphate
Phenylene-tetrakis (6-methylphenyl) phosphate, 1,3-phenylene-tetrakis (2-methylphenyl) phosphate, 1,3-phenylene-tetrakis (3-methylphenyl) phosphate, 1,
3-phenylene-tetrakis (4-methylphenyl) phosphate, 1,3-phenylene-tetrakis (5-
Methylphenyl) phosphate, 1,3-phenylene-tetrakis (6-methylphenyl) phosphate,
4,4'-biphenylene-tetrakis (2-methylphenyl) phosphate, 4,4'-biphenylene-tetrakis (3-methylphenyl) phosphate, 4,4
'-Biphenylene-tetrakis (4-methylphenyl)
Phosphate esters, 4,4'-biphenylene-tetrakis (5-methylphenyl) phosphate, 4,4'-biphenylene-tetrakis (6-methylphenyl) phosphate, and the like, particularly 1,4-phenylene -Tetrakis (2,6-dimethylphenyl) phosphate, 1,3-phenylene-tetrakis (2,6-dimethylphenyl) phosphate, 4,4'-biphenylene-tetrakis (2,6-dimethylphenyl) phosphoric acid Acid ester, 1,4-phenylene-tetrakis (3-methylphenyl) phosphate, 1,3-phenylene-tetrakis (3-methylphenyl) phosphate, 4,4 ′
-Biphenylene-tetrakis (3-methylphenyl) phosphate is more preferred.

Specific examples of other condensed phosphate esters include resorcinol-bis (phenyl) phosphate oligomer. A specific example of the halogen-containing phosphoric acid ester is tris (tribromoneopentyl).
Phosphate and the like.

The method for producing the phosphate compound (III) is not particularly limited and can be obtained by a known method.

The amount of the phosphate compound (III) of the present invention is 1 to 30 parts by weight based on 100 parts by weight of the transparent thermoplastic resin.
Parts by weight, preferably 2 to 25 parts by weight. When the content of the phosphate compound (III) is less than 1 part by weight, the flame retardancy of the obtained flame retardant thermoplastic resin composition is not sufficient. Heat resistance is not enough.

In the present invention, the weight ratio {(II) / (III)} of the amount of the brominated aromatic triazine flame retardant (II) to the amount of the phosphate compound (III) is 1 or more. . When this ratio is less than 1, that is, when the amount of the phosphoric ester compound (III) added is larger than the amount of the brominated aromatic triazine-based flame retardant (II), the heat resistance of the obtained flame-retardant thermoplastic resin composition is low. not enough.

The monomers used for the graft copolymer (A) are 10 to 50% by weight of an aromatic vinyl monomer (b), 0 to 20% by weight of a vinyl cyanide monomer (c), 50 to 90% by weight of a saturated carboxylic acid alkyl ester monomer (d) and another copolymerizable vinyl monomer (e)
Preferably, it is comprised between 0 and 60% by weight. More preferably, 15 to 35% by weight of an aromatic vinyl monomer (b), 0 to 10% by weight of a vinyl cyanide monomer (c), 60% of an unsaturated carboxylic acid alkyl ester monomer (d) To 80% by weight, and other copolymerizable vinyl monomers (e)
0 to 40% by weight. The aromatic vinyl-based monomer (b), vinyl cyanide-based monomer (c), unsaturated carboxylic acid alkyl ester-based monomer (B) constituting the vinyl (co) polymer (B) in the present invention The composition of d) and other vinyl monomers (e) copolymerizable as required is not particularly limited, but is preferably an aromatic vinyl monomer in view of balancing transparency and impact resistance. Monomer (b) 10 to 50
% By weight, 0 to 20% by weight of a vinyl cyanide-based monomer (c), and an unsaturated carboxylic acid alkyl ester-based monomer (d)
50 to 90% by weight, and 0 to 60% by weight of another copolymerizable vinyl monomer (e). More preferably, 15 to 35% by weight of the aromatic vinyl monomer (b), 0 to 10% by weight of the vinyl cyanide monomer (c), and 60% of the unsaturated carboxylic acid alkyl ester monomer (d) To 80% by weight, and other copolymerizable vinyl monomers (e)
0 to 40% by weight.

The mixing ratio of the graft copolymer (A) and the vinyl (co) polymer (B) constituting the thermoplastic resin (I) of the present invention is from 10 to 60% by weight of the graft copolymer (A). Parts by weight, 40 to 90 parts by weight of the vinyl (co) polymer (B). If the amount of the graft copolymer (A) is less than 10 parts by weight or the amount of the vinyl (co) polymer (B) exceeds 90 parts by weight, the impact strength decreases. In addition, the graft copolymer (A) has 60
If the amount is more than 10 parts by weight, the melt viscosity increases and the moldability deteriorates. Preferably, the amount is 20 to 50 parts by weight of the graft copolymer (A) and 50 to 80 parts by weight of the vinyl (co) polymer (B).

The content of the rubbery polymer (a) in the graft copolymer (A) is not particularly limited.
80 parts by weight are preferred. If the amount is less than 20 parts by weight, the impact strength of the obtained transparent thermoplastic resin composition decreases, and if it exceeds 80 parts by weight, the melt viscosity increases and moldability deteriorates, which is not preferable. More preferably, the amount is 35 parts by weight to 60 parts by weight. It is not necessary that all of the monomer mixture compounded in the graft copolymer (A) be grafted by bonding to the rubbery polymer (a). They may be bonded together and contained as a non-grafted polymer. However, the graft ratio is preferably from 10 to 100%, particularly preferably from 20 to 50%. The reduced viscosity (ηsp / c) of the vinyl (co) polymer (B) in the present invention is not particularly limited, but may be 0.1 to
0.6 dl / g is preferred. In other cases, the impact resistance is reduced, or the melt viscosity is increased, and the moldability is likely to be deteriorated. More preferably, it is 0.3 to 0.5 dl / g.

The method for producing the graft copolymer (A) and the vinyl (co) polymer (B) in the present invention is not particularly limited, and may be any of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like. . There is no particular limitation on the method of charging the monomer, and initial batch charging, continuous charging of part or all of the monomer,
Alternatively, any method of partly or entirely charging the monomer may be used.

The method for producing the flame-retardant thermoplastic resin composition of the present invention is not particularly limited, and the thermoplastic resin (I),
It can be produced by melt-kneading a brominated aromatic triazine-based flame retardant (II) and a phosphate compound (III) with, for example, a Banbury mixer, roll, extruder, kneader or the like.

The flame retardant thermoplastic resin composition of the present invention is blended with various thermoplastic resins and elastomers within a range not to impair the object of the present invention, so that the performance as a molding resin composition is improved. Further improvements can be made.

The flame-retardant thermoplastic resin composition of the present invention may contain, if necessary, an antioxidant such as a hindered phenol-based compound, a sulfur-containing compound-based compound, a phosphorus-containing organic compound-based compound, a phenol-based compound, an acrylate-based compound. Heat stabilizers, UV stabilizers such as benzotriazoles, benzophenones, succinates, etc., various stabilizers such as organic nickel-based, hindered amine-based light stabilizers, etc., metal salts of higher fatty acids,
Lubricants such as higher fatty acid amides, phthalates,
Plasticizers such as phosphate esters, flame retardant aids such as antimony trioxide and antimony pentoxide, carbon black, pigments and dyes can also be added.

Furthermore, various reinforcing agents and fillers can be added to the flame-retardant thermoplastic resin composition of the present invention.

The substantially transparent flame-retardant thermoplastic resin composition obtained above can be used for injection molding, extrusion molding, blow molding, vacuum molding, compression molding and gas-assist molding. It can be molded by a known method used for molding, and is not particularly limited.

The flame-retardant thermoplastic resin composition of the present invention takes advantage of its excellent impact resistance, heat resistance, fluidity during molding, and flame retardancy to provide housings for OA equipment, home electric appliances, and the like. Suitable for parts.

[0041]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In Examples and Comparative Examples, all parts and percentages are by weight unless otherwise specified. The analysis method for the characteristics of the transparent flame-retardant thermoplastic resin will be described below.

(1) Refractive index A small amount of 1-bromonaphthalene was dropped on a sample to be measured, and the refractive index was measured using an Abbe refractometer under the following conditions.

Light source: sodium lamp D line Measurement temperature: 20 ° C.

(2) Weight Average Rubber Particle Size “Rubber Age Vol.88 p.484-
490 (1960) by E.I. Schmidt, P .;
H. And the sodium alginate method described in "Biddison". That is, utilizing the fact that the particle size of polybutadiene to be creamed differs depending on the concentration of sodium alginate, the cumulative weight fraction of the creamed weight ratio and the cumulative weight fraction of the sodium alginate concentration are 50%.
Is determined.

(3) Graft ratio Acetone was added to a predetermined amount (m) of the graft copolymer, and the mixture was refluxed for 3 hours. This solution was cooled to 8800 r / min (10000).
After centrifugation at G) for 40 minutes, insolubles were collected by filtration, and the insolubles were dried under reduced pressure at 60 ° C. for 5 hours, and the weight (n) was measured. The graft ratio was calculated from the following equation. Graft ratio (%) = {[(n)-(m) × L] / [(m) × L]}
× 100 Here, L is the rubber content of the graft copolymer.

(4) Reduced viscosity ηsp / c 200 ml of acetone was added to 1 g of the sample, refluxed for 3 hours, and the solution was centrifuged at 8,800 r / min (10000 G) for 40 minutes, and then the insoluble matter was filtered. The filtrate was concentrated on a rotary evaporator, and the precipitate (acetone-soluble matter) was dried under reduced pressure at 60 ° C. for 5 hours, and then dried at 0.4 g / 100 g.
ml (methyl ethyl ketone, 30 ° C.), and ηsp / c was measured using an Ubbelohde viscometer.

(5) Transparency evaluation method The haze value [%] of the square plate (thickness: 3 mm) was measured using a direct-reading haze meter manufactured by Toyo Seiki Co., Ltd. The lower the haze value, the better the transparency.

(6) Izod impact strength Measured according to ASTM D256 (12.7 mm notch, 23 ° C.).

(7) Flame retardancy: According to the UL94 standard, a vertical combustion test was performed on a 燃 焼 ″ × １ ／ ″ × 5 ″ combustion test piece, and a pass / fail judgment on Class V-2 was made.

(8) Heat resistance According to ASTM D648 (test thickness: 1/4 ", 1.
82 MPa load).

[Reference Example 1] Method for producing graft copolymer (A) 50 parts by weight of polybutadiene (weight average particle diameter 0.2 μm) (in terms of solid content) 0.5 parts by weight of potassium oleate 0.5 parts by weight of glucose Sodium pyrophosphate 0.5 parts by weight Ferrous sulfate 0.005 parts by weight Deionized water 120 parts by weight The above substances were charged into a polymerization vessel, and the temperature was raised to 65 ° C. while stirring. With the time when the internal temperature reached 65 ° C. as the start of polymerization, 50 parts by weight of a mixture composed of 70 parts of methyl methacrylate, 25 parts of styrene, 5 parts of acrylonitrile, and 0.3 part of t-dodecylmercaptan was continuously dropped over 5 hours. . In parallel, cumene hydroperoxide 0.25
, 2.5 parts of potassium oleate and 25 parts of pure water were continuously added dropwise over 7 hours to complete the reaction. The obtained graft copolymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to obtain a graft copolymer (A) A1. This graft copolymer (A) A
1 had a graft ratio of 45% and a reduced viscosity ηsp / c of 0.2.
It was 7 dl / g.

Reference Example 2 Vinyl (co) polymer (B)
In a stainless steel autoclave having a capacity of 20 L and equipped with a baffle and a Faudra type stirring blade, a methyl methacrylate / acrylamide copolymer (Japanese Patent Publication No. 45-24151) was used.
A solution prepared by dissolving 0.05 part in 165 parts of ion-exchanged water was stirred at 400 rpm, and the system was replaced with nitrogen gas. Next, the following mixture was added while stirring the reaction system, and the temperature was raised to 60 ° C. to initiate polymerization. Methyl methacrylate 70 parts by weight Styrene 25 parts by weight Acrylonitrile 5 parts by weight t-dodecylmercaptan 0.2 parts by weight 2,2'-azobisisobutyronitrile 0.4 parts by weight Raise the reaction temperature to 65 ° C. in 15 minutes After warming, 50
The temperature was raised to 100 ° C. over a minute. Thereafter, the reaction system was cooled, the polymer was separated, washed, and dried according to a conventional method to obtain a vinyl (co) polymer (B) B1. The reduced viscosity ηsp / c of this vinyl (co) polymer (B) B1 was 0.36 dl / g.

Reference Example 3 Brominated aromatic triazine flame retardant (II) "Pyroguard" SR245 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2,4,6-tris (2,4,6-tribromophenoxy) ) -1,3,5-Triazine Melting point = 230 ° C., 10% weight loss point by heat weight loss curve = 37
The 10% weight loss point in the 0 ° C. heat loss curve was determined by subjecting a sample to heat treatment in the range of 200 to 500 ° C. using a differential thermal weight loss analyzer, and measuring the 10% weight loss point from the weight loss curve.

[Reference Example 4] Phosphate ester compound (II
I) <III-1>"PX200" (Daichi Chemical Co., Ltd.)
1,3-phenylene-tetrakis (2,6-dimethylphenyl) phosphate <III-2>"PX201" (Daichi Chemical Industry Co., Ltd.)
1,4-phenylene-tetrakis (2,6-dimethylphenyl) phosphate <III-3>4,4'-biphenylene-tetrakis (2,6-dimethylphenyl) phosphate <III-4>" CR733S "(Daichi Chemical Industry Co., Ltd.)
Resorcinol bis (phenyl) phosphate oligomer <III-5>"CR900" (Daichi Chemical Co., Ltd.)
Tris (tribromoneopentyl) phospho-
G.

Reference Example 5 Brominated epoxy compound "Plasam" EP-100 (manufactured by Dainippon Ink and Chemicals, Inc.).

Examples 1 to 9 Graft copolymer (A), vinyl (co) polymer (B), brominated aromatic triazine flame retardant (II) and phosphate ester (III) shown in Reference Examples Was mixed at the mixing ratio shown in Table 1 and 40 m with vent was mixed.
m By melt-kneading and extruding with a single screw extruder,
A pellet-shaped substantially transparent flame-retardant thermoplastic resin composition was produced. Then, using an injection molding machine, a test piece was molded at a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C.
Physical properties were measured under the above conditions, and the obtained measurement results are shown in Table 1.

[0057]

[Table 1]

Comparative Examples 1 to 6 The graft copolymer (A), vinyl (co) polymer (B), brominated aromatic triazine flame retardant (II), phosphate ester (III) shown in Reference Examples ) And a brominated epoxy compound were mixed at the compounding ratios shown in Table 1, and the respective physical properties were measured in the same manner as in the examples. The measurement results are shown in Table 1.

The following is clear from the results in Table 1.
Each of the flame-retardant thermoplastic resin compositions of the present invention (Examples 1 to 9) has excellent balance of impact resistance, heat resistance, transparency (haze value) and flame retardancy.

On the other hand, when the amount of the vinyl (co) polymer (B) exceeds 90 parts by weight (Comparative Example 1), the impact resistance is inferior.

A brominated aromatic triazine-based flame retardant (II) with less than 2 parts by weight (Comparative Example 4) was inferior in flame retardancy, and a brominated aromatic triazine-based flame retardant (II) with more than 30 parts by weight (Comparative Example 5) was impact resistant. Inferior in properties and not preferred

A compound containing less than 1 part by weight of the phosphoric ester compound (III) (Comparative Example 2) is not preferable because of poor flame retardancy.

Further, those in which the weight ratio {(II) / (III)} of the amount of addition of the brominated aromatic triazine flame retardant (II) and the phosphate compound (III) is less than 1 (Comparative Example 3) are as follows: Poor heat resistance is not preferred.

When a brominated epoxy compound is used as a flame retardant (Comparative Example 6), transparency is lost.

[0065]

According to the present invention, by using a specific brominated flame retardant in combination with a phosphate ester, a substantially flame-retardant thermoplastic resin composition having both transparency and heat resistance can be obtained.

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Claims (7)

[Claims] 1. An aromatic vinyl monomer (b), a vinyl cyanide monomer (c) and an unsaturated carboxylic acid alkyl ester monomer (d) based on a rubbery polymer (a). And a graft copolymer (A) obtained by graft copolymerizing one or more monomers selected from other copolymerizable vinyl monomers (e), and an aromatic vinyl monomer ( b), at least one selected from vinyl cyanide monomers (c), unsaturated carboxylic acid alkyl ester monomers (d), and other copolymerizable vinyl monomers (e) And a vinyl-based polymer (B) composed of the above monomer in a weight ratio of 10:90 to 6:
With respect to 100 parts by weight of the thermoplastic resin (I) containing 0:40,
2 to 30 parts by weight of a brominated aromatic triazine flame retardant (II) and 1 to 30 parts by weight of a phosphoric ester compound (III) are added so that the weight ratio {(II) / (III)} becomes 1 or more. A flame-retardant thermoplastic resin composition comprising: 2. The rubbery polymer (a) has a weight-average particle diameter of 0.1 to 0.5 μm, and has a monomeric amount with the rubbery polymer (a) constituting the graft copolymer (A). The flame-retardant thermoplastic resin composition according to claim 1, wherein the weight ratio with the body is 20:80 to 80:20. 3. The graft copolymer (A) comprises 10 to 50% by weight of an aromatic vinyl monomer (b) and 0 to 20% by weight of a vinyl cyanide monomer (c). 50 to 90% by weight of an unsaturated carboxylic acid alkyl ester monomer (d) and another copolymerizable vinyl monomer (e) 0
The flame-retardant thermoplastic resin composition according to claim 1, which comprises about 60% by weight. 4. A monomer constituting the vinyl polymer (B) is 10 to 50% by weight of an aromatic vinyl monomer (b) and 0 to 20% by weight of a vinyl cyanide monomer (c). 50 to 90% by weight of an unsaturated carboxylic acid alkyl ester monomer (d) and another copolymerizable vinyl monomer (e) 0
The flame-retardant thermoplastic resin composition according to any one of claims 1 to 3, wherein the composition comprises from 60 to 60% by weight. 5. A brominated aromatic triazine flame retardant (II)
Has a melting point of 200 to 250 ° C.
5. The flame-retardant thermoplastic resin composition according to any one of items 1 to 4. 6. A brominated aromatic triazine flame retardant (II)
The flame-retardant thermoplastic resin composition according to any one of claims 1 to 5, wherein a 10% weight loss point according to a heat weight loss curve shows a characteristic of 300 ° C or more. 7. Brominated aromatic triazine flame retardant (II)
Is 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine.
The flame-retardant thermoplastic resin composition according to any one of the above.