JPH11246776A - Flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which has a large discharge amount in pelletization by an extruder when kneading with a resin, has good workability, and is excellent in flame retardancy. SOLUTION: (B) 1 to 50 parts by weight of a bromine compound (B) and 0 to 25 parts by weight of an inorganic flame retardant aid per 100 parts by weight of a thermoplastic resin, A flame-retardant resin composition comprising a specific bromine compound in the range of 1 to 2.5 at a time.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition having excellent workability.

[0002]

2. Description of the Related Art Organic polymer materials have good moldability, mechanical properties,
Due to its excellent electrical properties, it is used for various applications. Among them, high impact polystyrene (HI
Styrene resins such as PS) resin and ABS resin and polyolefin resins are inexpensive in addition to excellent properties, and are used in housings for home appliances and OA equipment, indoor and outdoor decorations, building materials, automobile parts, etc. It is widely used for various purposes.

[0003] Further, since these organic polymer materials are generally flammable, the burning of organic substances may cause disasters that threaten people's safety, and it is necessary to take measures to make such organic polymer materials nonflammable. With regard to flame retardancy of organic polymer materials, various regulations, including UL standards, have been strengthened and required.

[0004] In general, the flame retardation of an organic polymer material is performed by adding a flame retardant to the organic polymer material, blending a flame retardant resin, and using a reactive flame retardant monomer. Is carried out by a method such as reforming.

[0005] As a method for making a thermoplastic resin such as a styrene resin or a polyolefin resin flame retardant, various bromine-containing compounds have been conventionally proposed. For example, to make a styrene resin flame-retardant, hexabromocyclododecane (JP-B-43-29658), 2,2-bis [(3,5-dibromo-4-allyloxy) phenyl] propane ( JP-B-60-8019), 2,2-bis [@ 3,5-dibromo-4-
(2,3-dibromopropyloxy) @phenyl] propane (JP-A-60-240750, etc.), bis [{3,5-dibromo-4- (2,3-dibromopropyloxy)} phenyl] sulfone ( JP-A-60-24
No. 0750) is blended with such a resin, and 2,2-bis [@ 3,5-dibromo- is used as a flame retardant for making a polyolefin resin flame-retardant.
4- (2,3-dibromopropyloxy) @phenyl]
Propane (Japanese Patent Publication No. 5-82856, etc.), bis [{3,5-dibromo-4- (2,3-dibromopropyloxy)} phenyl] sulfone (Japanese Patent Publication No. 50-35)
No. 103) is known to be incorporated into such a resin. However, such a flame retardant has a low discharge rate in kneading with the resin, particularly in pelletization by an extruder, is inferior in workability, and has low productivity. There is a disadvantage that it becomes.

[0006]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies with the aim of providing a flame-retardant thermoplastic resin composition having excellent processability. It has been found that by controlling once within a specific range, a flame-retardant resin composition having a high discharge rate, excellent workability, and high productivity can be obtained in pelletization by an extruder when kneading with a resin. The present invention has been reached.

[0007]

That is, according to the present invention, (B) 1 to 50 parts by weight of a bromine compound and (C) an inorganic flame retardant aid per 100 parts by weight of a thermoplastic resin.
The bromine compound has a uniformity of 1 to 25 parts by weight.
A flame-retardant resin composition is provided, which is a bromine compound represented by the following formula (1) in the range of 2.5.

[0008]

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(Where m, n, p, and q are integers of 1 to 6, and Ar ¹ and Ar ² may be the same or different, and may be a divalent aromatic having 5 to 16 carbon atoms) Y is a kind selected from methylene, propylene, isopropylidene, isobutylidene, cyclohexylidene, sulfone, ketone and a single bond, and R ¹ and R ² are each a saturated hydrocarbon having 2 to 6 carbon atoms. Group.)

The thermoplastic resin (A) used in the present invention includes, for example, polyolefin resins, polystyrene resins, polyvinyl chloride resins, polyamide resins, polyester resins, polycarbonate resins, polyphenylene ether resins, and the like. Among them, polyolefin resins and polystyrene resins are preferably used.

The polyolefin resin is a homopolymer or a copolymer of olefins such as ethylene, propylene and butene, or a copolymer with a component copolymerizable with these olefins. Polypropylene, ethylene-vinyl acetate copolymer,
Ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-α-olefin copolymer, ethylene-propylene copolymer and propylene-butene copolymer, etc. Among them, polypropylene is preferably used.

The polystyrene resin is a resin containing a vinyl aromatic monomer as a constituent component. Examples of the vinyl aromatic monomer include styrene, o-methylstyrene and p-methylstyrene.
-Nuclear alkyl-substituted styrenes such as -methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, and p-tert-butylstyrene, and α-alkyls such as α-methylstyrene and α-methyl-p-methylstyrene Examples include a halogen-substituted styrene such as substituted styrene, monobromostyrene, dibromostyrene, and tribromostyrene. Specifically, polystyrene, polymethylstyrene, rubber-modified styrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-acryl rubber-styrene copolymer Polymer (AAS resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin), methyl methacrylate-butadiene-styrene copolymer (MBS
HIPS and ABS resins are preferable, and HIPS is particularly preferably used.

[0013] Such a rubber-modified styrene resin (HIPS)
Is a polymer in which a rubber-like polymer is dispersed in a particle form in a matrix made of a polystyrene resin, and in the presence of the rubber-like polymer, styrene and, if necessary, a vinyl monomer copolymerizable therewith. By subjecting the monomer mixture to known bulk polymerization, bulk suspension polymerization, solution polymerization or emulsion polymerization. The polymerization method may be one-stage polymerization or multi-stage polymerization. Examples of the diene rubber component forming this rubbery polymer include polybutadiene, polyisoprene, styrene-butadiene copolymer,
Rubbers such as butadiene-isoprene copolymer, ethylene-propylene copolymer, and natural rubber are preferably used, and the ratio is preferably 5 to 80% by weight in the HIPS resin component.

The ABS resin is a graft copolymer obtained by graft-polymerizing an aromatic vinyl compound component and a vinyl cyanide compound component capable of graft copolymerization with a diene rubber component as a base. Examples of the diene rubber component include polybutadiene and styrene-butadiene copolymer.Examples of the aromatic vinyl compound component grafted to these diene rubber components include styrene and α.
-Methylstyrene, p-methylstyrene, alkoxystyrene, halogenated styrene and the like, among which styrene is preferably used, and examples of the vinyl cyanide compound component include acrylonitrile, methacrylonitrile, chloroacrylonitrile, and the like. Among them, acrylonitrile is preferably used.
Further, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, maleic anhydride, N-substituted maleimide, and the like can be used. Such a graft copolymer,
It may be produced by any polymerization method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization, and the grafting method may be a single-stage graft or a multi-stage graft. Further, a blend of a vinyl copolymer obtained by separately copolymerizing the aromatic vinyl compound component and the vinyl cyanide compound component with a graft copolymer can also be preferably used.

Among these thermoplastic resins, as described above, polypropylene and HIPS are preferably used. In particular, polypropylene is preferably used because of its excellent flame retardancy. These thermoplastic resins can be used alone or in combination of two or more.

The bromine compound (B) used in the present invention is
A bromine compound represented by the above formula (1) having a uniformity of 1 to 2.5. M, n, p, and q in the formula (1) are integers of 1 to 6, preferably 1 to 4,
r ¹ and Ar ² may be the same or different and are a divalent aromatic hydrocarbon group having 5 to 16 carbon atoms, preferably a phenyl group, a tolyl group, a xylyl group or a naphthyl group;
Is one selected from methylene, propylene, isopropylidene, isobutylidene, cyclohexylidene, sulfone, ketone and a single bond, preferably one selected from methylene, isopropylidene, isobutylidene, cyclohexylidene, sulfone and a single bond , R ¹ and R ² are each a saturated hydrocarbon group having 2 to 6 carbon atoms, preferably an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group.

As the bromine compound represented by the formula (1), specifically, 2,2-bis [3,5-dibromo-4]
-(2,3-dibromopropyloxy) phenyl] propane, 2,2-bis [3,5-dibromo-4- (2,3
-Dibromo-2-methylpropyloxy) phenyl] propane, 2,2-bis [3,5-dibromo-4- (2,
3-dibromobutyloxy) phenyl] propane, 2,
2-bis [3,5-dibromo-4- (3,4-dibromobutyloxy) phenyl] propane, 2,2-bis [3,5-dibromo-4- (2,3-dibromopentyloxy) phenyl] Propane, 2,2-bis [3,5-
Dibromo-4- (4,5-dibromopentyloxy) phenyl] propane, 2,2-bis [3,5-dibromo-
4- (2,3,4,5-tetrabromopentyloxy)
Phenyl] propane;

Bis [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] sulfone, bis [3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl] sulfone, bis [3,5-dibromo-4- (2,3- Dibromobutyloxy) phenyl] sulfone, bis [3,5-dibromo-4- (3,4-dibromobutyloxy) phenyl] sulfone, bis [3,5-dibromo-4- (2,3-dibromopentyloxy) Phenyl] sulfone, bis [3,5-dibromo-4- (4,5-dibromopentyloxy) phenyl] sulfone, bis [3,5-dibromo-4- (2,3,4,5-tetrabromopentyloxy) ) Phenyl] sulfone;

1,1-bis [3,5-dibromo-4-
(2,3-dibromopropyloxy) phenyl] ethane, 1,1-bis [3,5-dibromo-4- (2,3-
Dibromo-2-methylpropyloxy) phenyl] ethane, 1,1-bis [3,5-dibromo-4- (2,3-
Dibromobutyloxy) phenyl] ethane, 1,1-bis [3,5-dibromo-4- (3,4-dibromobutyloxy) phenyl] ethane, 1,1-bis [3,5-dibromo-4- ( 2,3-dibromopentyloxy) phenyl] ethane, 1,1-bis [3,5-dibromo-4-
(4,5-dibromopentyloxy) phenyl] ethane, 1,1-bis [3,5-dibromo-4- (2,3,
4,5-tetrabromopentyloxy) phenyl] ethane;

Bis [3,5-dibromo-4- (2,3-
Dibromopropyloxy) phenyl] methane, bis [3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy) phenyl] methane, bis [3,5
-Dibromo-4- (2,3-dibromobutyloxy) phenyl] methane, bis [3,5-dibromo-4- (3,
4-dibromobutyloxy) phenyl] methane, bis [3,5-dibromo-4- (2,3-dibromopentyloxy) phenyl] methane, bis [3,5-dibromo-
4- (4,5-dibromopentyloxy) phenyl] methane, bis [3,5-dibromo-4- (2,3,4,5
-Tetrabromopentyloxy) phenyl] methane;

[3,3 ', 5,5'-tetrabromo-
4,4 '-(1,2-dibromoethyloxy)] biphenyl, [3,3', 5,5'-tetrabromo-4,4 '
-(2,3-dibromopropyloxy)] biphenyl,
[3,3 ', 5,5'-tetrabromo-4,4'-
(2,3-dibromo-2-methylpropyloxy)] biphenyl, [3,3 ', 5,5'-tetrabromo-4,
4 '-(2,3-dibromobutyloxy)] biphenyl, [3,3', 5,5'-tetrabromo-4,4'-
(3,4-dibromobutyloxy)] biphenyl,
[3,3 ', 5,5'-tetrabromo-4,4'-
(2,3-dibromopentyloxy)] biphenyl,
[3,3 ', 5,5'-tetrabromo-4,4'-
(4,5-dibromopentyloxy)] biphenyl,
[3,3 ', 5,5'-tetrabromo-4,4'-
(2,3,4,5-tetrabromopentyloxy)] biphenyl;

2,2-bis [4,6,8-tribromo-
5- (2,3-dibromopropyloxy) α-naphthyl] propane, 2,2-bis [4,6,7-tribromo-5- (2,3-dibromopropyloxy) β-naphthyl] propane, 2, 2-bis [4,6,8-tribromo-5- (2,3-dibromo-2-methylpropyloxy) α-naphthyl] propane, 2,2-bis [4,6
7-tribromo-5- (2,3-dibromo-2-methylpropyloxy) β-naphthyl] propane, 2,2-bis [4,6,8-tribromo-5- (2,3-dibromobutyloxy) α-naphthyl] propane, 2,2-bis [4,6,7-tribromo-5- (2,3-dibromobutyloxy) β-naphthyl] propane, 2,2-bis [4,6,8-tribromo -5- (3,4-dibromobutyloxy) α-naphthyl] propane, 2,2-bis [4,6,7-tribromo-5- (3,4-dibromobutyloxy) β-naphthyl] propane, , 2-bis [4,6,8-tribromo-5- (2,3-dibromopentyloxy) α-naphthyl] propane, 2,2-bis [4,6,7-tribromo-5- (2,3 -Dibromopentyloxy) β-naphthyl Propane, 2,2-bis [4,6,8-tribromo-5- (4,5-dibromopentyloxy) α-naphthyl] propane, 2,2-bis [4,6,7-tribromo-5- ( 4,5-dibromopentyloxy) β-naphthyl] propane, 2,2-bis [4,6,8-tribromo-5- (2,3,4,5-tetrabromopentyloxy) α-naphthyl] propane,
2,2-bis [4,6,7-tribromo-5- (2,
3,4,5-tetrabromopentyloxy) β-naphthyl] propane;

Bis [4,6,8-tribromo-5-
(2,3-dibromopropyloxy) α-naphthyl] sulfone, bis [4,6,7-tribromo-5- (2
3-dibromopropyloxy) β-naphthyl] sulfone, bis [4,6,8-tribromo-5- (2,3-dibromo-2-methylpropyloxy) α-naphthyl] sulfone, bis [4,6,7 -Tribromo-5- (2,
3-dibromo-2-methylpropyloxy) β-naphthyl] sulfone, bis [4,6,8-tribromo-5-
(2,3-dibromobutyloxy) α-naphthyl] sulfone, bis [4,6,7-tribromo-5- (2,3
-Dibromobutyloxy) β-naphthyl] sulfone,
Bis [4,6,8-tribromo-5- (3,4-dibromobutyloxy) α-naphthyl] sulfone, bis [4,6,7-tribromo-5- (3,4-dibromobutyloxy) β- Naphthyl] sulfone, bis [4,
6,8-tribromo-5- (2,3-dibromopentyloxy) α-naphthyl] sulfone, bis [4,6,7
-Tribromo-5- (2,3-dibromopentyloxy) β-naphthyl] sulfone, bis [4,6,8-tribromo-5- (4,5-dibromopentyloxy) α
-Naphthyl] sulfone, bis [4,6,7-tribromo-5- (4,5-dibromopentyloxy) β-naphthyl] sulfone, bis [4,6,8-tribromo-5
-(2,3,4,5-tetrabromopentyloxy) α
-Naphthyl] sulfone, bis [4,6,7-tribromo-5- (2,3,4,5-tetrabromopentyloxy) β-naphthyl] sulfone;

1,1-bis [4,6,8-tribromo-
5- (2,3-dibromopropyloxy) α-naphthyl] ethane, 1,1-bis [4,6,7-tribromo-
5- (2,3-dibromopropyloxy) β-naphthyl] ethane, 1,1-bis [4,6,8-tribromo-
5- (2,3-dibromo-2-methylpropyloxy)
α-naphthyl] ethane, 1,1-bis [4,6,7-tribromo-5- (2,3-dibromo-2-methylpropyloxy) β-naphthyl] ethane, 1,1-bis [4
6,8-tribromo-5- (2,3-dibromobutyloxy) α-naphthyl] ethane, 1,1-bis [4,6
7-tribromo-5- (2,3-dibromobutyloxy) β-naphthyl] ethane, 1,1-bis [4,6,8
-Tribromo-5- (3,4-dibromobutyloxy)
α-naphthyl] ethane, 1,1-bis [4,6,7-tribromo-5- (3,4-dibromobutyloxy) β-
Naphthyl] ethane, 1,1-bis [4,6,8-tribromo-5- (2,3-dibromopentyloxy) α-naphthyl] ethane, 1,1-bis [4,6,7-tribromo-5 -(2,3-dibromopentyloxy) β-naphthyl] ethane, 1,1-bis [4,6,8-tribromo-5- (4,5-dibromopentyloxy) α-naphthyl] ethane, 1,1 -Bis [4,6,7-tribromo-
5- (4,5-dibromopentyloxy) β-naphthyl] ethane, 1,1-bis [4,6,8-tribromo-
5- (2,3,4,5-tetrabromopentyloxy)
α-naphthyl] ethane, 1,1-bis [4,6,7-tribromo-5- (2,3,4,5-tetrabromopentyloxy) β-naphthyl] ethane;

Bis [4,6,8-tribromo-5-
(2,3-dibromopropyloxy) α-naphthyl] methane, bis [4,6,7-tribromo-5- (2,3-
Dibromopropyloxy) β-naphthyl] methane, bis [4,6,8-tribromo-5- (2,3-dibromo-
2-methylpropyloxy) α-naphthyl] methane, bis [4,6,7-tribromo-5- (2,3-dibromo-2-methylpropyloxy) β-naphthyl] methane,
Bis [4,6,8-tribromo-5- (2,3-dibromobutyloxy) α-naphthyl] methane, bis [4
6,7-tribromo-5- (2,3-dibromobutyloxy) β-naphthyl] methane, bis [4,6,8-tribromo-5- (3,4-dibromobutyloxy) α-naphthyl] methane, Bis [4,6,7-tribromo-5-
(3,4-dibromobutyloxy) β-naphthyl] methane, bis [4,6,8-tribromo-5- (2,3-dibromopentyloxy) α-naphthyl] methane, bis [4,6,7- Tribromo-5- (2,3-dibromopentyloxy) β-naphthyl] methane, bis [4,6
8-tribromo-5- (4,5-dibromopentyloxy) α-naphthyl] methane, bis [4,6,7-tribromo-5- (4,5-dibromopentyloxy) β-naphthyl] methane, bis [ 4,6,8-tribromo-5-
(2,3,4,5-tetrabromopentyloxy) α-
Naphthyl] methane, bis [4,6,7-tribromo-5
-(2,3,4,5-tetrabromopentyloxy) β
-Naphthyl] methane and the like.

Among them, 2,2-bis [{3,5-dibromo-4- (2,3-dibromopropyloxy)} phenyl] propane and 2,2-bis [{3,5-dibromo-
4- (2,3-dibromo-2-methylpropyloxy) phenyl] propane, bis [{3,5-dibromo-4- (2,3-dibromopropyloxy)} phenyl] methane, bis [{3 5-dibromo-4- (2,3
-Dibromo-2-methylpropyloxy) @phenyl]
Methane, bis [{3,5-dibromo-4- (2,3-dibromopropyloxy)} phenyl] sulfone, bis [{3,5-dibromo-4- (2,3-dibromo-2-)
Methylpropyloxy)｝ phenyl] sulfone,
{3,3 ', 5,5'-tetrabromo-4,4'-
(2,3-dibromopropyloxy)｝ biphenyl,
{3,3 ', 5,5'-tetrabromo-4,4'-
(2,3-dibromo-2-methylpropyloxy)} biphenyl and {3,3 ′, 5,5′-tetrabromo-
4,4 '-(1,2-Dibromoethyloxy)} biphenyl is preferred, and 2,2-bis [{3,5-dibromo-
4- (2,3-dibromopropyloxy) @phenyl]
Propane, bis [｛3,5-dibromo-4- (2,3-
Dibromopropyloxy) {phenyl] methane and bis [{3,5-dibromo-4- (2,3-dibromopropyloxy)} phenyl] sulfone are more preferred,
Particularly, 2,2-bis [｛3,5-dibromo-4- (2,3
-Dibromopropyloxy) {phenyl] propane is preferably used.

The uniformity referred to in the present invention is to create a cumulative particle size distribution graph based on weight, and accumulated from a small particle diameter, the cumulative weight and the particle diameter d ₆₀ at which the cumulative weight becomes 60% 10 %, The particle diameter d ₁₀ where d ₆₀ / d ₁₀
Is calculated by the following equation. The closer this value is to 1, the more uniform the particle size.

In the bromine compound (B) of the present invention, the value of such uniformity is from 1 to 2.5, and from 1 to 2.3.
Is preferable, and 1 to 1.7 are more preferable. If the uniformity of the bromine compound exceeds 2.5, the processability when blended with the resin and melt-kneaded will be inferior.

The average particle size of the bromine compound is 0.1.
The range of 2 mm to 1 mm is preferable, and 0.25 mm to 0.
The range of 9 mm is more preferable, and the bromine compound particles within this range have excellent dispersibility when blended with a resin as a flame retardant.

In the present invention, as a method for obtaining a bromine compound having a uniformity of 1 to 2.5, for example, (1) powder of a bromine compound is heated at a temperature of 50 ° C. or more by a hot-air drying apparatus. A method of treating, (2) a method of equalizing the particle diameter of the bromine compound powder by sieving or the like, and the like.
Above all, the method (1) is preferably employed because there is no loss of the bromine compound and the operation is simple.

With such a hot air heating type drying apparatus, 50 ° C.
The bromine compound powder treated at the above temperature may be obtained by any method. For example, a good solvent solution of a bromine compound is added to a poor solvent, and a powder of the bromine compound precipitated or a good solvent is evaporated from a good solvent solution of the bromine compound by a rotary evaporator or the like, and the remaining bromine compound is removed. A powder of a bromine compound or the like obtained by pulverizing a mass of the above is used.

The bromine compound powder has an average particle size of 0.0
It is preferably from 0.01 to 0.2 mm, and from 0.01 to 0.1 mm.
mm is more preferable. The bromine compound powder is 50
When the powder is in contact with hot air at a temperature of ℃ or more, the surface of the powder is partially melted, which serves as a binder, and the powders effectively adhere to each other, and the particle size is uniform. It is thought that the bromine compound particles easily formed.

The drying apparatus used in such a method includes:
It is a hot-air heating type drying apparatus, and a conduction heating type drying apparatus such as a reduced-pressure drying apparatus cannot obtain bromine compound particles having a specific uniformity used in the present invention. Examples of such a hot-air heating type drying apparatus include a box-type dryer of a material standing type hot-air heating method, a tunnel dryer and a band dryer of a material transfer type hot-air heating method. A method of circulating the heated gas in the dryer is also preferably used.
Air or an inert gas is preferably used as the heated gas used in the hot air heating type drying apparatus,
Examples of the inert gas include helium, argon, and nitrogen, and nitrogen is particularly preferably used.

It is preferable to use a vibration type hot air heating type drying apparatus among the hot air heating type drying apparatuses.
Even when granulation is carried out for a long time, there is no problem of fusion to the inner wall due to stagnation of the bromine compound, and it is possible to obtain bromine compound particles having a narrower particle size distribution and a more uniform particle size. Can be.

In the above method (1), it is necessary to maintain the temperature in the hot air drying apparatus at 50 ° C. or higher. When the temperature is lower than 50 ° C., the bromine compound powder does not adhere to each other and does not form granules. Further, the temperature in the hot air heating type drying apparatus is preferably a temperature lower than the melting point of the bromine compound powder to be used, since there is no problem of forming a large mass. The pressure in the drying device is not particularly limited, but it is preferable to granulate the bromine compound at normal pressure.

When the bromine compound powder is 2,2-bis [ビ ス 3,
In the case of powder of 5-dibromo-4- (2,3-dibromopropyloxy) {phenyl] propane, the temperature in the hot-air drying apparatus is preferably 50 ° C to 120 ° C,
A temperature of 0 ° C to 115 ° C is more preferred, and a temperature of 55 ° C to 110 ° C.
A temperature of ° C. is particularly preferred. When the powder of the bromine compound is a powder of bis [{3,5-dibromo-4- (2,3-dibromopropyloxy)} phenyl] methane, the inside of the hot air heating type drying apparatus is at 50 ° C to 100 ° C. Is preferably 50 ° C to 95 ° C, more preferably 55 ° C to 9 ° C.
A temperature of 0 ° C. is particularly preferred. In the case of bis [{3,5-dibromo-4- (2,3-dibromopropyloxy)} phenyl] sulfone powder, a temperature of 50 to 170 ° C. is preferable in a hot air heating type drying apparatus, and 55 ° C. ℃ -16
A temperature of 5C is more preferred, and a temperature of 60C to 160C is particularly preferred.

The time for granulating the bromine compound powder in the hot air heating type drying apparatus is preferably 10 minutes or more, more preferably 10 minutes to 30 hours, and more preferably 15 minutes to 2 hours.
0 hours is more preferred.

The air velocity of the heated gas in the hot air heating type drying apparatus is preferably 0.1 to 5 m / sec.
Ｍ3 m / sec is more preferable. When the wind speed is within this range, bromine compound particles having a specific uniformity can be easily obtained.

In such a method, the volume ratio of the bromine compound in the hot air drying device is preferably in the range of 0.1 to 90% in terms of volume ratio with respect to the internal volume of the hot air heating drying device.
The range of 0.2 to 80% is more preferable, and 0.3 to 60%
Is more preferable, and the range of 0.5 to 30% is particularly preferable. Within this range, bromine compound particles having a specific uniformity can be easily obtained, and the productivity is excellent.

In the flame-retardant resin composition of the present invention, the inorganic flame-retardant auxiliary (C) used as required is one which increases flame retardancy by interaction with a bromine compound. There are, specifically, antimony trioxide, antimony pentoxide, boron trioxide, zinc borate, red phosphorus and the like, among which antimony trioxide and antimony pentoxide are particularly preferred.

The proportion of each component in the flame-retardant resin composition is 1 to 50 parts by weight, preferably 1.5 to 30 parts by weight, more preferably 1.5 to 30 parts by weight, based on 100 parts by weight of the thermoplastic resin. To 15 parts by weight, more preferably 2.5 to 1 part by weight.
0 parts by weight is more preferable, and 3 to 8 parts by weight is particularly preferable. If the amount is less than 1 part by weight, the flame-retardant effect is low, and 50
When the amount is more than the weight part, the thermal stability of the flame-retardant resin composition is lowered, and the mechanical properties are lowered.
Further, based on 100 parts by weight of the thermoplastic resin, the inorganic flame retardant is 0 to 25 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.2 to 15 parts by weight, .
Particularly preferred is 3 to 10 parts by weight. If the amount is more than 25 parts by weight, the mechanical properties deteriorate, which is not preferable.

The flame-retardant resin composition of the present invention is prepared by blending these components in the above-mentioned mixing ratio, and using a Henschel mixer, a tumbler mixer, a super mixer, a Banbury mixer, a kneader, a roll, a single screw extruder, a twin screw extruder. It is manufactured by appropriately using a method of mixing and kneading with a machine or the like.

The flame-retardant resin composition of the present invention may further contain a colorant, a pigment, a stabilizer, a plasticizer, a lubricant, an ultraviolet absorber, a filler, a reinforcing agent, a foaming agent, and other additives as required. Can be blended.

The flame-retardant resin composition obtained according to the present invention is extremely useful as a material for various uses including housings for home electric appliances and OA equipment, indoor and outdoor decorations, building materials, automobile parts and the like.

[0045]

Hereinafter, the present invention will be described in detail with reference to Examples.
Of course, it is not limited to this. The evaluation was performed according to the following methods (1) to (3).

(1) Average particle size, uniformity Samples were prepared for 200, 100, 60, 20, 16, 10,
After sieving using a 5,3.5 mesh sieve, a cumulative particle size distribution graph based on weight is created, and the particle size at which the cumulative weight becomes 50% is determined. did. In addition, average particle size 0.1 mm that cannot be measured by sieving
In the following, the average particle size was similarly obtained from a cumulative particle size distribution graph based on the obtained weight using a Coulter Counter LS230 type particle size distribution analyzer. Also,
The uniformity is calculated by accumulating the created cumulative particle size distribution graph from the smallest particle size, and calculating the particle size d ₆₀ where the cumulative weight becomes 60% and the particle size d ₁₀ where the cumulative weight becomes 10%. It was calculated by the formula of d ₆₀ / d ₁₀ .

(2) Discharge Amount When the resin composition is melt-kneaded and pelletized by a twin-screw extruder, the weight of the pellet discharged in 2 minutes is weighed, and the amount converted per hour is discharged. Amount (kg / h)
And

(3) Flame Retardancy The flame retardancy was evaluated using a 1/8 inch thick test piece according to the vertical combustion test method specified in UL-94 of the UL standard. NotV of the evaluation result means a rejected product that does not satisfy the V rank. Also, JISK-72
The oxygen index (OI value) according to 01 was measured.

Synthesis Example 1 300 g of 2,2-bis {(3,5-dibromo-4-allyloxy) phenyl} propane was placed in a glass container equipped with a stirrer, condenser, thermometer, dropping funnel and ice bath. (0.48 mol)
And 511 g of methylene chloride were added and dissolved. next,
The solution was cooled to 2 ° C. and, with stirring, bromine 161.
3 g (1.01 mol) was dropped from the dropping funnel over 30 minutes. At the end of the dropwise addition, the temperature of the reaction solution was 15 ° C. After the completion of the dropwise addition, the reaction solution was further stirred for 30 minutes to complete the bromine addition reaction.

Next, after reducing excess bromine in the reaction solution with 120 g of a 15% by weight aqueous solution of sodium bisulfite,
The produced hydrogen bromide was neutralized using a 25% by weight aqueous sodium hydroxide solution. Thereafter, a methylene chloride layer was separated from the solution, and about 90% of the methylene chloride was evaporated and removed from the methylene chloride layer.
The reaction product was precipitated by adding mL, and the precipitate was filtered to remove a massive solid. This lump solid was pulverized in a mortar, dried under reduced pressure of 5 mmHg at 80 ° C. for 10 hours, and 2,2-bis [で 3,5-dibromo-4- (2,3-dibromopropyl) having an average particle diameter of 0.05 mm. Oxy) {phenyl] propane was obtained.

[Synthesis Example 2] In Synthesis Example 1, 2,2-
Instead of 300 g of bis {(3,5-dibromo-4-allyloxy) phenyl} propane, bis {(3,5-dibromo-4-allyloxy) phenyl} sulfone 311
g [0.48 mol], except that bis [ビ ス 3,5
-Dibromo-4- (2,3-dibromopropyloxy) {phenyl] sulfone was obtained.

[Synthesis Example 3] In Synthesis Example 1, 2,2-
287 g of bis {(3,5-dibromo-4-allyloxy) phenyl} methane instead of 300 g of bis {(3,5-dibromo-4-allyloxy) phenyl} propane
(0.48 mol), except that bis [$ 3,5-
Dibromo-4- (2,3-dibromopropyloxy)
[Phenyl] methane was obtained.

[Adjustment Example 1] A vibration-type hot air circulating heating dryer having a volume of 90 L (Q manufactured by Tamagawa Machinery Co., Ltd.) with an internal temperature of 80 ° C. and nitrogen flowing at a wind speed of 0.9 m / sec.
AD), 2,2-bis [{3,5-dibromo-4- (2,3-dibromopropyloxy)} phenyl] propane (hereinafter, referred to as a synthetic resin having an average particle diameter of 0.05 mm obtained in Synthesis Example 1).
1 kg of powder (sometimes abbreviated as TBA-BP) (1.7 L in capacity) was charged. After drying for 40 minutes, TBA-
The BP was taken out. The average particle size of the obtained TBA-BP granules was 0.7 mm, and the uniformity was 1.3.

[Adjustment Example 2] A hot air circulating heating box-type drier having an inner volume of 90 L (Tabayespec Co., Ltd., LC) in which the internal temperature is kept at 80 ° C. and nitrogen is flowing at a wind speed of 0.9 m / sec.
-112), the average particle diameter obtained in Synthesis Example 1 was 0.05 m.
m 2,2-bis [{3,5-dibromo-4- (2,3
[Dibromopropyloxy) {phenyl] propane powder (1 kg, 1.7 L). After drying for 40 minutes, TBA-BP was taken out. Obtained TBA-BP
The average particle size of the granules was 0.8 mm, and the uniformity was 1.9.

[Adjustment Example 3] A hot air circulating-heating box-type dryer having an inner volume of 90 L (Tabayspec Co., Ltd., LC) in which the internal temperature was maintained at 57 ° C. and nitrogen was flowing at a wind speed of 0.9 m / sec.
-112), the average particle diameter obtained in Synthesis Example 1 was 0.05 m.
m 2,2-bis [{3,5-dibromo-4- (2,3
[Dibromopropyloxy) {phenyl] propane powder (1 kg, 1.7 L). After drying for 40 minutes, TBA-BP was taken out. Obtained TBA-BP
The average particle size of the granules was 0.3 mm, and the uniformity was 2.2.

[Adjustment Example 4] A vibration-type hot air circulating heating dryer having an internal volume of 90 L (Q manufactured by Tamagawa Machinery Co., Ltd.) in which the internal temperature was maintained at 80 ° C. and nitrogen was flowing at a wind speed of 0.9 m / sec.
AD), bis [{3,5-dibromo-4- (2,3-dibromopropyloxy)} phenyl] sulfone (hereinafter referred to as TBS) having an average particle size of 0.08 mm obtained in Synthesis Example 2.
1 kg of powder (capacity: 1.4)
L). After drying for 40 minutes, TBS-BP was taken out. The average particle size of the obtained TBS-BP granules was 0.3 mm, and the uniformity was 1.7.

[Adjustment Example 5] A vibration-type hot air circulating heating dryer having an internal volume of 90 L (Q manufactured by Tamagawa Machinery Co., Ltd.) having an internal temperature of 80 ° C. and a nitrogen flow of 0.9 m / sec.
AD), bis [{3,5-dibromo-4- (2,3-dibromopropyloxy)} phenyl] methane (hereinafter TBF-B) having an average particle size of 0.02 mm and obtained in Synthesis Example 3.
1 kg of powder (capacity: 1.8 L)
Was put. After drying for 40 minutes, the TBF-BP was taken out. The average particle size of the obtained TBF-BP granules is 0.4
mm and uniformity were 1.5.

[Adjustment Example 6] A hot air circulating-heating box-type dryer having an inner volume of 90 L (Tabayspec Co., Ltd.) with an internal temperature of 42 ° C. and a nitrogen flow of 0.9 m / sec.
-112), the average particle diameter obtained in Synthesis Example 1 was 0.05 m.
m 2,2-bis [{3,5-dibromo-4- (2,3
[Dibromopropyloxy) {phenyl] propane powder (1 kg, 1.7 L). After drying for 40 minutes, TBA-BP was taken out. Obtained TBA-BP
Was 0.06 mm and the uniformity was 3.6.

[Adjustment Example 7] A 90 L hot air circulating heating box-type dryer (LC manufactured by Tabai Speck Co., Ltd.) in which the internal temperature was kept at 42 ° C. and nitrogen was flowing at a wind speed of 0.9 m / sec.
-112), the average particle size obtained in Synthesis Example 2 was 0.08 m.
1 kg of bis [{3,5-dibromo-4- (2,3-dibromopropyloxy)} phenyl] sulfone powder of m
(1.4 L capacity). After drying for 40 minutes,
BS-BP was taken out. The average particle size of the obtained TBS-BP was 0.09 mm, and the uniformity was 4.5.

[Adjustment Example 8] In Adjustment Example 1, the internal volume 9
Adjustment example 1 except that a 90 L heat transfer heating type vacuum box type dryer (LCV-232 made by Tabai Espec Co.) was used in place of the 0 L vibrating hot air circulating heating dryer.
The same operation as described above was performed. The average particle size of the obtained TBA-BP was 0.10 mm, and the uniformity was 2.7.

[Example 1] High impact polystyrene resin [HIPS; Stylon 492 manufactured by Asahi Kasei Corporation)
R-H27-71], 100 parts of the bromine compound obtained in Preparation Example 1 and 0.6 part of antimony trioxide were added, and mixed with a tumbler-type blender, followed by a twin-screw extruder [Ikekai Iron Works Co., Ltd. ) PCM-30], pelletize at a cylinder temperature of 160 ° C, and then use an injection molding machine [Ltd.
A test piece was molded at a molding temperature of 230 ° C. using a Meiki Seisakusho SJ-25B. The discharge amount in pelletization was calculated, and the flame retardancy was evaluated using the obtained test pieces. The results are shown in Table 1.

[Second Embodiment] In the first embodiment, the first adjustment example is used.
Except for using the bromine compound obtained in Preparation Example 2 in place of the bromine compound obtained in Example 1, a test piece was molded in the same manner as in Example 1, and the discharge amount in pelletization was calculated. The flame retardancy was evaluated using the obtained test pieces, and the results are shown in Table 1.

[Third Embodiment] In the first embodiment, the first adjustment example is used.
A test piece was molded in the same manner as in Example 1 except that the bromine compound obtained in Preparation Example 3 was used instead of the bromine compound obtained in the above, and the discharge amount in pelletization was calculated. The flame retardancy was evaluated using the obtained test pieces, and the results are shown in Table 1.

[Fourth Embodiment] In the first embodiment, the first adjustment example is used.
A test piece was molded in the same manner as in Example 1 except that antimony trioxide was not used, except that 6 parts of the bromine compound obtained in the above was used as 10 parts, and the discharge amount in pelletization was calculated. The flame retardancy was evaluated using the test pieces, and the results are shown in Table 1.

Example 5 A test piece was molded in the same manner as in Example 1 except that 1.0 part of antimony pentoxide was used instead of 0.6 part of antimony trioxide. The discharge amount in pelletization was calculated, and the flame retardancy was evaluated using the obtained test pieces. The results are shown in Table 1.

[Sixth Embodiment] In the first embodiment, the first adjustment example will be described.
A test piece was molded in the same manner as in Example 1 except that the bromine compound obtained in Preparation Example 4 was used instead of the bromine compound obtained in the above, and the discharge amount in pelletization was calculated. The flame retardancy was evaluated using the obtained test pieces, and the results are shown in Table 1.

[Seventh Embodiment] In the first embodiment, the first adjustment example is used.
A test piece was molded in the same manner as in Example 1 except that the bromine compound obtained in Preparation Example 5 was used instead of the bromine compound obtained in the above, and the discharge amount in pelletization was calculated. The flame retardancy was evaluated using the obtained test pieces, and the results are shown in Table 1.

Example 8 Polypropylene resin [PP;
8 parts of the bromine compound obtained in Preparation Example 1 and 4 parts of antimony trioxide were added to 100 parts of K-1016 (manufactured by Chisso Petrochemical Industry Co., Ltd.) and mixed with a tumbler-type blender, followed by a twin-screw extruder [ Ikegai Iron Works Co., Ltd. PCM-30]
Then, a test piece was formed at a molding temperature of 190 ° C. using an injection molding machine [SJ-25B manufactured by Meiki Seisakusho Co., Ltd.]. The discharge amount in pelletization was calculated, and the flame retardancy was evaluated using the obtained test pieces. The results are shown in Table 1.

[Comparative Example 1] In Example 1, the adjustment example 1
A test piece was formed in the same manner as in Example 1 except that the bromine compound obtained in Preparation Example 6 was used instead of the bromine compound obtained in the above, and the discharge amount in pelletization was calculated. The flame retardancy was evaluated using the obtained test pieces, and the results are shown in Table 1.

Comparative Example 2 Adjustment Example 1 in Example 1
A test piece was formed in the same manner as in Example 1 except that the bromine compound obtained in Preparation Example 8 was used instead of the bromine compound obtained in the above, and the discharge amount in pelletization was calculated. The flame retardancy was evaluated using the obtained test pieces, and the results are shown in Table 1.

[Comparative Example 3] In the embodiment 1, the adjustment example 1
A test piece was molded in the same manner as in Example 1 except that 10 parts of the bromine compound obtained in Preparation Example 6 was used instead of 6 parts of the bromine compound obtained in Example 1, and no antimony trioxide was used. The discharge amount in the chemical conversion was calculated, and the flame retardancy was evaluated using the obtained test pieces. The results are shown in Table 1.

Comparative Example 4 Adjustment Example 1 in Example 1
Except that the bromine compound obtained in Preparation Example 6 was used in place of the bromine compound obtained in Example 1, and that 1.0 part of antimony pentoxide was used instead of 0.6 part of antimony trioxide.
Test pieces were molded in the same manner as in Example 1, the discharge amount in pelletization was calculated, and the flame retardancy was evaluated using the obtained test pieces. The results are shown in Table 1.

[Comparative Example 5] In Example 1, the adjustment example 1
A test piece was formed in the same manner as in Example 1 except that the bromine compound obtained in Preparation Example 7 was used instead of the bromine compound obtained in the above, and the discharge amount in pelletization was calculated. The flame retardancy was evaluated using the obtained test pieces, and the results are shown in Table 1.

[Comparative Example 6] In Adjustment Example 1 in Example 8,
Except that the bromine compound obtained in Preparation Example 6 was used instead of the bromine compound obtained in the above, a test piece was molded in the same manner as in Example 8, and the discharge amount in pelletization was calculated. The flame retardancy was evaluated using the obtained test pieces, and the results are shown in Table 1.

[0075]

[Table 1]

[0076]

Industrial Applicability The flame-retardant resin composition of the present invention has a high discharge rate, is excellent in workability, is highly productive, and has good flame-retardant performance when pelletized by an extruder when kneading the resin. Being a composition, its industrial effect is exceptional.

Claims (6)

[Claims] 1. A composition comprising (B) 1 to 50 parts by weight of a bromine compound and (C) 0 to 25 parts by weight of an inorganic flame retardant, based on 100 parts by weight of a thermoplastic resin. A flame-retardant resin composition comprising a bromine compound represented by the following formula (1) having a degree of uniformity of 1 to 2.5. Embedded image (Where m, n, p, and q are integers of 1 to 6,
Ar ¹ and Ar ² may be the same or different and are a divalent aromatic hydrocarbon group having 5 to 16 carbon atoms, and Y is methylene, propylene, isopropylidene, isobutylidene,
Cyclohexylidene, sulfone, ketone and a single bond are selected, and R ¹ and R ² each have 2 carbon atoms.
To 6 saturated hydrocarbon groups. ) 2. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin is a polystyrene resin or a polyolefin resin. 3. The flame-retardant resin composition according to claim 1, wherein the bromine compound is a compound represented by the following formula (2). Embedded image (Where m, n, p, and q are integers of 1 to 4,
Ar ¹ and Ar ² may be the same or different and are a phenyl group, a tolyl group, a xylyl group or a naphthyl group;
Y is a kind selected from methylene, isopropylidene, isobutylidene, cyclohexylidene, sulfone and single bond, and R ¹ and R ² are each a kind selected from ethyl group, propyl group, isopropyl group, butyl group and isobutyl group. is there. ) 4. The bromine compound is 2,2-bis [素 3,5
-Dibromo-4- (2,3-dibromopropyloxy)} phenyl] propane, 2,2-bis [{3,5-
Dibromo-4- (2,3-dibromo-2-methylpropyloxy) {phenyl] propane, bis [{3,5-dibromo-4- (2,3-dibromopropyloxy)} phenyl] methane, bis [} 3,5-dibromo-4-
(2,3-dibromo-2-methylpropyloxy) @phenyl] methane, bis [@ 3,5-dibromo-4-
(2,3-dibromopropyloxy) @phenyl] sulfone, bis [{3,5-dibromo-4- (2,3-dibromo-2-methylpropyloxy)} phenyl] sulfone, {3,3 ', 5 , 5'-Tetrabromo-4,
4 '-(2,3-dibromopropyloxy)} biphenyl, {3,3', 5,5'-tetrabromo-4,4'-
(2,3-dibromo-2-methylpropyloxy)} biphenyl and {3,3 ′, 5,5′-tetrabromo-
The flame-retardant resin composition according to claim 1, which is a kind of compound selected from 4,4 '-(1,2-dibromoethyloxy) オ キ シ biphenyl. 5. The method according to claim 1, wherein the inorganic flame retardant is a thermoplastic resin.
The flame-retardant resin composition according to claim 1, wherein the amount is 0.1 to 20 parts by weight based on parts by weight. 6. An inorganic flame-retardant auxiliary agent comprising antimony trioxide,
The flame-retardant resin composition according to claim 1, which is at least one compound selected from the group consisting of antimony pentoxide, boron trioxide, zinc borate, and red phosphorus.