JPH08231861A - Flame-retardant thermoplastic resin composition and flame retardant - Google Patents

Abstract

PURPOSE: To obtain a flame-retardant thermoplastic resin composition excellent in both flame-retardant effect and mold release by mixing a thermoplastic resin with a flame retardant comprising a specified modified halogenated epoxy resin. CONSTITUTION: This composition comprises a thermoplastic resin and a compound having a structure derived by blocking the epoxy groups of a halogenated epoxy resin with a monobasic carboxylic acid having a halogen atom and a long-chain alkyl group in the molecule (this compound being the flame retardant of this invention). This compound is desirably one having a structure derived by blocking the epoxy groups of a halogenated epoxy resin with an aromatic monocarboxylic acid having a halogen atom and a long-chain alkyl group in the aromatic nucleus more desirably one having a structure derived by blocking these epoxy groups with a monoalkyl ester of a halogenated aromatic dicarboxylic acid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant plastic resin composition which is excellent in mold releasability of a molded article from a mold, and a flame retardant which imparts good releasability to a thermoplastic resin.

[0002]

2. Description of the Related Art In recent years, halogenated epoxy resins have been widely used as flame retardants for thermoplastic resin compositions because of their excellent flame retardant effect. Flame retardant resin compositions containing such flame retardants are widely used. Since the compounded flame retardant has a high adhesiveness to the metal part of the mold, the molded product deteriorates the releasability of the molded product from the mold.

Therefore, as a conventional flame retardant for a thermoplastic resin having improved mold releasability, for example, JP-A-4-34 has been known.
Japanese Patent No. 8167 discloses a technique in which a compound obtained by blocking a terminal epoxy group of a halogenated epoxy resin with a long-chain aliphatic carboxylic acid is used as a flame retardant.

[0004]

However, the above-mentioned Japanese Unexamined Patent Application Publication No.
The flame retardant disclosed in JP-A-348167 has an improved mold releasing effect, but is inferior in flame retardant effect to the unmodified halogenated epoxy resin.

The problem to be solved by the present invention is to provide a flame retardant having a low adhesion to a metal part such as a molding machine or a mold without deteriorating the flame retardant effect, and an excellent flame retardant effect and a mold. It is intended to provide a flame-retardant thermoplastic resin composition having both releasability.

[0006]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to solve the above-mentioned problems, as a flame retardant for a thermoplastic resin, a halogenated epoxy resin or an epoxy group of a halogenated epoxy resin has a halogen atom. A flame retardant effect is obtained by using a composition containing a compound having a structure blocked with a monovalent carboxylic acid having a long-chain alkyl group in the molecular structure (hereinafter abbreviated as halogenated carboxylic acid monoester). It was found that the mold releasability from the mold can be improved without deteriorating the temperature and the present invention has been completed.

That is, the present invention comprises (A) a thermoplastic resin,
Flame-retardant thermoplastic resin characterized in that the epoxy group of the halogenated epoxy resin contains a compound (B) having a structure in which the epoxy group is blocked by a monovalent carboxylic acid having a halogen atom and a long-chain alkyl group in the molecular structure. The resin composition and the epoxy group of the halogenated epoxy resin contain a compound having a structure blocked with a monovalent carboxylic acid compound having a halogen atom and a long-chain alkyl group in the molecular structure. Flame retardant.

The halogenated epoxy resin which can be used in the present invention is not particularly limited, and examples thereof include halogenated bisphenol type epoxy resin, halogenated phenol novolac type epoxy resin, halogenated cresol novolac type epoxy resin, halogenated resorcin type epoxy resin. Resin, halogenated hydroquinone type epoxy resin, halogenated bisphenol A novolac type epoxy resin, halogenated methylresorcin type epoxy resin, halogenated resorcinol novolak type epoxy resin and the like,
Usually, a halogenated bisphenol type epoxy resin having an average degree of polymerization of 0 to 50 is preferable.

Specific examples of the halogenated bisphenol constituting the halogenated bisphenol type epoxy resin include dibromobisphenol A, tetrabromobisphenol A, dichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, tetrabromobisphenol F and dichloro. Bisphenol F,
Examples thereof include tetrachlorobisphenol F, dibromobisphenol S, tetrabromobisphenol S, dichlorobisphenol S, tetrachlorobisphenol S, and the like.

The monovalent carboxylic acid having a halogen atom and a long-chain alkyl group in the molecular structure used in the present invention is not particularly limited, and may be a halogenated alkylcarboxylic acid or a halogen atom on the aromatic nucleus. Examples thereof include aromatic monocarboxylic acids having a long-chain alkyl group, monoalkyl esters of halogenated alkylenedicarboxylic acids, and the like. Among them, the reactivity with epoxy groups is good, and the monovalent carboxylic acid itself is produced. Aromatic monocarboxylic acids having a halogen atom and a long-chain alkyl group on the aromatic nucleus are preferred from the standpoint of ease of use, and monoalkyl esters of halogenated aromatic dicarboxylic acids are particularly preferred.

The monoalkyl ester of the halogenated aromatic dicarboxylic acid is not particularly limited, but specifically, a half ester obtained by reacting the halogenated aromatic dicarboxylic acid with a long chain aliphatic alcohol is used. Can be mentioned. As the halogenated aromatic dicarboxylic acid, for example, monobromoterephthalic acid, dibromoterephthalic acid,
Tribromoterephthalic acid, tetrabromoterephthalic acid,
Examples thereof include monochloroterephthalic acid, dichloroterephthalic acid, trichloroterephthalic acid, tetrachloroterephthalic acid, and the like. Among them, tetrabromoterephthalic acid is preferable because of its remarkable flame retardant effect.

Further, as the long-chain aliphatic alcohol to be reacted with the halogenated aromatic dicarboxylic acid, an aliphatic alcohol having 3 or more carbon atoms is preferable from the viewpoint of excellent effect of reducing metal adhesion, for example, propionol, Butanol, pentanol, hexanol, heptanol,
Octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, icosanol, henicosanol, docosanol, triacontanol, tetracontanol and the like are preferable. . Of these, those having 4 to 20 carbon atoms, especially those having 4 to 4 carbon atoms
12 is more preferable.

The compound (B) used in the present invention is a monovalent carboxylic acid in which the epoxy group in the above halogenated epoxy resin has a halogen atom and a long-chain alkyl group in its molecular structure (hereinafter, simply referred to as "1 The carboxylic acid is abbreviated as "), and the production method is not specified, and a halogenated epoxy resin and 1
The reaction may be performed with a carboxylic acid by heating. For example, when a halogenated bisphenol type epoxy resin made of halogenated bisphenol and epihalohydrin as a raw material is used as the halogenated epoxy resin, the halogenated epoxy resin and the monovalent epoxy resin are used. A method of reacting with a carboxylic acid,
Examples thereof include a method in which a halogenated bisphenol is reacted with a halogenated bisphenol to give a high molecular weight and then a monovalent carboxylic acid is reacted, and a method in which a halogenated epoxy resin is reacted with a monovalent carboxylic acid and a halogenated bisphenol. .

The reaction conditions for any of the above reactions are:
Although not particularly limited, 1 in the presence or absence of a catalyst
It is preferable to heat and react at 00 to 230 ° C. Further, the catalyst that can be used is not particularly limited, for example, as the catalyst, for example, an alkali metal hydroxide such as sodium hydroxide, a tertiary amine such as dimethylbenzylamine,
Imidazoles such as 2-ethyl-4methylimidazole, quaternary ammonium salts such as tetramethylammonium chloride, phosphonium salts such as ethyltriphenylphosphonium iodide, and phosphines such as triphenylphosphine can be used. The reaction solvent is not particularly necessary and may not be used.

In the above method, when the monovalent carboxylic acid is heated and reacted, the halogenated carboxylic acid monoester may be used in combination with a sealing agent such as halogenated phenols.

The amount of the monovalent carboxylic acid used is not particularly limited, but it is preferable that the number of functional groups of the carboxyl group is equal to or smaller than the number of functional groups of the epoxy group in the halogenated epoxy resin. Is based on the total weight of halogenated epoxy resin and monovalent carboxylic acid,
It is preferable to use the monovalent carboxylic acid in the range of 0.01 to 10% by weight from the viewpoint of the effect of releasing the metal, the thermal stability during molding, and the heat distortion temperature.

The compound (B) thus obtained, that is, the flame retardant of the present invention, has a halogenated epoxy resin which is a halogenated bisphenol type epoxy resin, and
When the monovalent carboxylic acid is a monoalkyl ester of a halogenated aromatic dicarboxylic acid, for example, the following general formula 1
One having a structure represented by

[0018]

Embedded image (In the general formula 1, R represents a methylene group, a 2,2-propylidene group and a phenylmethylene group, X represents a bromine atom and a chlorine atom, and R ′ represents an aliphatic hydrocarbon group having 3 to 20 carbon atoms. , R "represents a 2-hydroxy-1,3-propylene group, n is an integer of 0 to 50, and m is an integer of 1 to 4.)

Next, the thermoplastic resin (A) usable in the present invention is not particularly limited, and examples thereof include polystyrene, rubber-modified polystyrene (HIPS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin). , Acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin) and other styrene resins, polyethylene, polypropylene and other polyolefin resins, polybutylene terephthalate (PBT)
Resin), polyester resin such as polyethylene terephthalate (PET resin), polycarbonate resin, polyamide resin, polyphenylene oxide (PPO) resin, and alloy of PPO resin and polystyrene, ABS
Alloy of resin and polycarbonate resin, ABS resin and P
Examples thereof include thermoplastic resins such as alloys of BT resin, alloys of polycarbonate resin and polyester resin, alloys of polycarbonate resin and polyamide resin.

The flame retardant of the present invention is the above thermoplastic resin (A).
Not only is it applicable to thermosetting resins such as epoxy resins, phenol resins, polyurethane resins, etc., but especially in the case of thermoplastic resins, the effect of improving the moldability becomes remarkable.

The blending amount of the flame retardant (compound (B)) of the present invention with respect to these thermoplastic resins (A) is not particularly limited, but is usually 1 to 50 parts by weight with respect to 100 parts by weight of the thermoplastic resin. In particular, 5 to 30 parts by weight is preferable because the flame retardant effect is high and the deterioration of physical properties such as impact resistance is small.

In the present invention, a flame-retardant thermoplastic resin finally obtained by further using a compound (C) having a structure in which the epoxy group of the halogenated epoxy resin is blocked with a halogenated phenol. The thermal stability of the composition can be significantly improved. The halogenated epoxy resin used here is not particularly limited, and any of those exemplified as the raw material components of the compound (B) can be used. Specifically, the halogenated bisphenol type epoxy resin, halogenated epoxy resin, etc. Phenol novolac type epoxy resin, halogenated cresol novolac type epoxy resin, halogenated resorcinol type epoxy resin,
Examples thereof include halogenated hydroquinone type epoxy resin, halogenated bisphenol A novolac type epoxy resin, halogenated methylresorcin type epoxy resin, halogenated resorcinol novolac type epoxy resin and the like.

Examples of the halogenated phenol to be reacted with the halogenated epoxy resin include monobrominated phenol, dibromophenol, tribromophenol, monochlorophenol, dichlorophenol, trichlorophenol, etc., but particularly flame retardant effect is obtained. Tribromophenol is preferable because it is remarkable.

When the compound (C) is used, when the compound (B) is melt-kneaded with the thermoplastic resin (A),
Although it may be introduced into the extruder, the compound (B) and the compound (C) are melt-kneaded and pelletized in advance, and then the thermoplastic resin (A) as a flame retardant component and further addition Mixing with the agent component is preferable from the viewpoint that the effect of improving the thermal stability becomes remarkable.

The flame-retardant thermoplastic resin composition of the present invention preferably contains a flame-retardant aid (D) in order to further enhance the flame-retardant effect. Examples of the flame retardant aid (D) include antimony compounds such as antimony trioxide, antimony tetraoxide and antimony pentoxide, tin compounds such as tin oxide and tin hydroxide, molybdenum oxides such as molybdenum oxide and ammonium molybdate. Examples thereof include compounds, zirconium compounds such as zirconium oxide and zirconium hydroxide, and boron compounds such as zinc borate and barium metaborate.

The blending amount of these flame retardant aids (D) is usually 0.2 to 25 parts by weight with respect to 100 parts by weight of the thermoplastic resin, and among them, physical properties such as flame retardancy and impact resistance are small. 1 to 15 parts by weight is preferable in terms of

The resin composition of the present invention comprises, for example, a thermoplastic resin, a flame retardant, and, if necessary, a flame retardant auxiliary agent and other additive components in a predetermined amount, and a mixer such as a Henschel mixer or a tumbler mixer. It can be easily produced by pre-mixing with a mixer, mixing with an extruder, a kneader, a heat roll, a Banbury mixer, or the like.

In the resin composition of the present invention, other flame retardants such as bromine flame retardants, chlorine flame retardants, and phosphorus flame retardants are used as long as the releasability from the mold during injection molding is not significantly impaired. You may mix a flame retardant, a nitrogen-based flame retardant, an inorganic flame retardant, etc.,
Further, if necessary, an ultraviolet absorber, a light stabilizer, a release agent, a lubricant, a colorant, a plasticizer, a filler, a foaming agent, an impact resistance improver, a compatibilizer, a coupling agent, a heat stabilizer, an oxidation agent. Inhibitors, glass fibers, carbon fibers, reinforcing materials such as aramid fibers and the like can be added.

[0029]

EXAMPLES The present invention will be described in more detail with reference to examples and comparative examples, but the scope of the present invention is not limited to these examples.

All parts and% in the examples are based on weight, and various tests are evaluated by the following measuring methods. (1) Softening point test (ring-and-ball type) It was measured according to JIS K-7234. (2) Epoxy group content test It is the reciprocal of the epoxy equivalent (g / eq) measured according to JIS K-7236, and is a value expressed in eq / g unit. (3) Heat distortion temperature test According to ASTM D-648, a load of 18.6 kg /
It was measured in cm 2.

The unit of measurement is expressed in ° C. (4) Izod impact strength test (with notch) Notched thickness 1 / based on ASTM D-256
It measured using the 4-inch test piece. The unit of measurement is k
Expressed in g · cm / cm. (5) Flammability test (UL-94) Subject 9 of Underwriters Laboratories
Based on method No. 4, length 5 inches x width 1/2 inches x
The measurement was performed using five test pieces having a thickness of 1/8 inch. (6) Mold releasability test (metal adhesion) The metal adhesion was evaluated by measuring the resistance pressure received when ejecting the molded product from the mold by the ejection rod of the molding machine during injection molding. Specifically, a box-shaped molded product (with dimensions of 200 mm width × 100 mm depth × 50 height)
mm × thickness 2.35 mm), the pellet of the well-dried flame-retardant resin composition is put into the 10 ounce injection molding machine equipped with a mold capable of molding, and injection molding is performed, and the molded product is molded into a metal mold. After cooling in the mold, the mold was opened, and the maximum resistance pressure when the ejection rod of the molding machine advanced to push out the ejector plate was measured by the pressure sensor. The metal adhesion of the flame-retardant resin composition was evaluated from the resistance pressure (unit: kg / cm2) at this time.

A pressure sensor (NSP-2C type manufactured by Technoplus Co., Ltd.) is attached between a plate for driving the ejector rod and a hydraulic cylinder for moving the plate,
The pressure exerted on the stick was detected.

When the metal adhesion is low, the resistance pressure value becomes small and the obtained molded product is not deformed. Therefore, the metal adhesion was evaluated according to the following ranks.

Judgment Resistance pressure value Appearance of molded product ◎: 25 kgf / cm ² or less No deformation or whitening at all ○: 26 to 35 kgf / cm ² Almost no deformation or whitening △: 36 to 45 kgf / cm ^{2 in} part Deformation and whitening difficult for practical use ×: 46 to 65 kgf / cm ² Deformation and whitening not possible for practical use × ×: 66 kgf / cm ² or more remarkable deformation and whitening

The molding conditions are as follows. Cylinder temperature: 220 for ABS and HIPS
~ 230 ° C ABS / PC polymer alloy, 240 ° C PBT, 250-260 ° C PBT / PC polymer alloy, 250 ° C Injection pressure: 1400-500 kgf / cm2 Mold temperature: 60-80 ° C Injection Time / cooling time: 10 seconds / 20 seconds

Next, the flame retardant used in the present invention and the flame retardant to be compared were produced by Examples 1 to 10 and Comparative Examples 1 to 3.

Production Example 1 372 g of tetrabromophthalic anhydride and 680 g of 1-butanol were placed in a 2 liter flask equipped with a reflux tube, a thermometer and a stirrer, the inside was replaced with nitrogen gas, and then the contents were heated, The reaction was carried out for 4 hours under reflux. After the reaction was completed, unreacted 1-butanol was distilled off under reduced pressure to obtain 401 g of tetrabromophthalic acid monobutyl ester as a white solid.

Production Example 2 In the same manner as in Example 1 except that 372 g of tetrabromophthalic anhydride and 990 g of 1-heptanol were used, 423 g of white tetrabromophthalic acid monoheptyl ester was obtained.

Production Example 3 In the same manner as in Example 1 except that 372 g of tetrabromophthalic anhydride and 1200 g of 1-octanol were used, 419 g of white tetrabromophthalic acid monooctyl ester was obtained.

Example 1 Diglycidyl ether of tetrabromobisphenol A [EPICLON 15 manufactured by Dainippon Ink and Chemicals, Inc.]
2, epoxy equivalent 360g / eq, bromine content 48%]
720.0 g and tetrabromobisphenol A (hereinafter T
BA (abbreviated as BA) 150.0 g and 2,4,6-tribromophenol (abbreviated as TBP hereinafter) 438.0 g were put in a 1 liter separable flask equipped with a thermometer and a stirrer, and the inside was filled with nitrogen gas. After the replacement, the contents are heated and melted, and at 10O 0 C, a 10% aqueous solution of sodium hydroxide 1.3.
After adding g, it was made to react at 150-180 degreeC for 12 hours.

Further, 20.3 g of tetrabromophthalic acid monobutyl ester (carboxyl equivalent 540 g / eq)
Was added and reacted at 150 ° C. for 6 hours. After the reaction, the reaction product was poured into a stainless pan, cooled, and then pulverized to obtain a pale yellow flame retardant powder. This is designated as flame retardant A. The property values of this flame retardant are shown in Table 1.

Example 2 720.0 g of EPICLON 152 and TBA150.
0 g and TBP 414.0 g and tetrabromophthalic acid monoheptyl ester (carboxyl group equivalent 554 g / e
q) Flame retardant powder was obtained in the same manner as in Example 1 except that 64.0 g was used. This is designated as flame retardant B. The property values of this flame retardant are shown in Table 1.

Example 3 720.0 g of EPICLON 152 and TBA150.
0 g, TBP 418.0 g and tetrabromophthalic acid monooctyl ester (carboxyl group equivalent 596 g / e
q) Flame retardant powder was obtained in the same manner as in Example 1 except that 57.5 g was used. This is designated as flame retardant C. The property values of this flame retardant are shown in Table 1.

Example 4 720.0 g of EPICRON 152 and TBA150.
0 g, TBP 424.0 g, and tetrabromophthalic acid monobutyl ester (carboxyl group equivalent 540 g / eq)
Flame retardant powder was obtained in the same manner as in Example 1 except that 43.0 g was used. This is designated as flame retardant D. The property values of this flame retardant are shown in Table 1.

Example 5 720.0 g of EPICLON 152 and TBA150.
0g and TBP388.0g and sodium hydroxide 10%
After preliminarily reacting at 110 to 120 ° C. for 6 hours with 1.3 g of an aqueous solution and then reacting at 150 to 180 ° C., further 98.4 g of tetrabromophthalic acid monobutyl ester (carboxyl group equivalent 540 g / eq). Flame retardant powder was obtained in the same manner as in Example 1 except that the reaction was carried out at 150 ° C. This is designated as flame retardant E. The property values of this flame retardant are shown in Table 1.

Example 6 720.0 g of EPICLON 152 and TBA223.
2 g and tetrabromophthalic acid monoheptyl ester 6
Flame retardant powder was obtained in the same manner as in Example 1 except that 4.0 g was used. This is designated as flame retardant F. The property values of this flame retardant are shown in Table 1.

Example 7 720.0 g of EPICLON 152 and TBA490.
0 g and 0.4 g of a 10% aqueous solution of sodium hydroxide were used, the reaction was carried out at 150 to 230 ° C. for 12 hours, and then the reaction was carried out with tetrabromophthalic acid monobutyl ester 58.4 g. Flame retardant powder was obtained in the same manner as in Example 1. This is designated as flame retardant G. The property values of this flame retardant are shown in Table 2.

Example 8 720.0 g of EPICLON 152 and TBA223.
A flame retardant powder was obtained in the same manner as in Example 1 except that 2 g and 0.3 g of a 10% aqueous solution of sodium hydroxide were used. 300 g of this flame retardant powder and B600 flame retardant
g was melt-mixed at 150 ° C. for 1 hour, the contents were poured into a stainless pan, cooled and pulverized to obtain a pale yellow flame retardant powder. This is designated as flame retardant H. The property values of this flame retardant are shown in Table 2.

Comparative Example 1 EPICLON 152 720.0 g and TBA 150.
Example 1 except that 0 g, TBP450.0 and 1.3 g of a 10% aqueous solution of sodium hydroxide were used.
Flame retardant powder was obtained in the same manner as in. This is designated as flame retardant I. The property values of this flame retardant are shown in Table 2.

Comparative Example 2 720.0 g of EPICLON 152 and TBA223.
A flame retardant powder was obtained in the same manner as in Example 1 except that 2 g and 0.3 g of a 10% aqueous solution of sodium hydroxide were used. This is designated as flame retardant J. The property values of this flame retardant are shown in Table 2.

Comparative Example 3 EPICLON 152 (720.0 g) and TBA490.
A flame retardant powder was obtained in the same manner as in Example 1 except that 0 g and 0.3 g of a 10% aqueous solution of sodium hydroxide were used and the reaction was carried out at 150 to 230 ° C. for 12 hours.
This is designated as flame retardant K. The property value of this flame retardant is
Shown in the table.

Comparative Example 4 720.0 g of EPICLON 152 and TBA150.
0 g, TBP 374.0 g, stearic acid 66.0 g and sodium hydroxide 10% aqueous solution 1.3 g,
A flame retardant powder was obtained in the same manner as in Example 4, except that the reaction was carried out at 150 to 230 ° C for 12 hours. This is designated as flame retardant L. The property values of this flame retardant are shown in Table 2.

Comparative Example 5 EPICLON 152 (720.0 g) and TBA506.
0g, stearic acid 26.0g, and sodium hydroxide 1
1% at 150-230 ° C. with 0.3 g of 0% aqueous solution
Flame retardant powder was obtained in the same manner as in Example 4 except that the reaction was performed for 2 hours. This is designated as flame retardant M. The property values of this flame retardant are shown in Table 2.

The results of Examples 1 to 8 and the results of Comparative Examples 1 to 5 are shown in Tables 1 and 2.

[0055]

[Table 1]

[0056]

[Table 2]

[0057]

[Table 3]

Examples 9 to 23 and Comparative Examples 6 to 21 The respective components were blended in the compositions shown in Tables 4 to 9, premixed with a tumbler mixer, and pelletized with a 30 mmφ twin-screw extruder. A resin composition was obtained. Then
A test piece is prepared by a 1 ounce injection molding machine and subjected to a heat distortion temperature test, an Izod impact test and a flammability test, and further, a limit injection molding test is conducted by a 5 ounce injection machine.
A mold releasability test was conducted using an ounce injection molding machine. The test results are shown in Tables 4 to 9.

The cylinder set temperature of the extruder is HI.
In the case of the polymer alloy of PS, ABS resin and ABS / PC, it was performed at 210 to 230 ° C, and in the case of the polymer alloy of PBT and PBT / PC, it was performed at 230 to 250 ° C.

In the table, ABS resin is "Cevian V-300" manufactured by Daicel Chemical Industries, Ltd., and HIPS is rubber modified styrene resin "GH-" manufactured by Dainippon Ink and Chemicals, Inc.
9650 ", PC resin is Mitsubishi Gas Chemical Co., Ltd. polycarbonate resin" Iupilon S-2000 ", PBT
Resin is "Barox 310" manufactured by Nippon GE Plastics Co., Ltd., and antimony trioxide is "P" manufactured by Nippon Seiko Co., Ltd.
ATOX-C ".

[0061]

[Table 4]

[0062]

[Table 5]

[0063]

[Table 6]

[0064]

[Table 7]

[0065]

[Table 8]

[0066]

[Table 9]

[0067]

EFFECTS OF THE INVENTION According to the present invention, a flame retardant having a low adhesiveness to a metal part such as a molding machine or a mold without deteriorating the flame retardant effect, and an excellent flame retardant effect and mold release. A flame-retardant thermoplastic resin composition having both properties can be provided.

Further, the flame-retardant thermoplastic resin composition of the present invention has remarkably reduced metal adhesion, so that the molding time can be shortened and the productivity in molding can be improved.

Claims (13)

[Claims] 1. A compound (B) having a structure in which a thermoplastic resin (A) and an epoxy group of a halogenated epoxy resin are blocked with a monovalent carboxylic acid having a halogen atom and a long-chain alkyl group in its molecular structure. ) And a flame-retardant thermoplastic resin composition. 2. The compound (B) is a compound having a structure in which an epoxy group of a halogenated epoxy resin is blocked with an aromatic monocarboxylic acid containing a halogen atom and a long chain alkyl group on an aromatic nucleus. The composition of claim 1. 3. The composition according to claim 2, wherein the compound (B) has a structure in which the epoxy group of the halogenated bisphenol type epoxy resin is blocked with a monoalkyl ester of a halogenated aromatic dicarboxylic acid. 4. The compound (B) has a structure in which an epoxy group of a halogenated bisphenol type epoxy resin is blocked with a monoalkyl ester of a halogenated aromatic dicarboxylic acid and a halogenated phenol. The composition according to 3. 5. In addition to the thermoplastic resin (A) and the compound (B), the epoxy group of the halogenated epoxy resin further contains a compound (C) having a structure blocked with a halogenated phenol. 4. The composition according to any one of 4. 6. The composition according to claim 5, wherein the compound (C) has a structure in which an epoxy group of a halogenated bisphenol type epoxy resin is blocked with tribromophenol. 7. The flame-retardant thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (A) is a styrene resin or a polymer alloy containing the styrene resin as one component. 8. The flame-retardant thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyester resin or a polymer alloy containing the polyester resin as one component. . 9. A flame-retardant auxiliary agent (D) is further contained.
The flame-retardant thermoplastic resin composition according to any one of items 1 to 8. 10. The epoxy group of the halogenated epoxy resin contains a compound having a structure blocked with a monovalent carboxylic acid compound having a halogen atom and a long-chain alkyl group in the molecular structure. Flame retardants. 11. The flame retardant according to claim 10, wherein the monovalent carboxylic acid compound is an aromatic monocarboxylic acid containing a halogen atom and a long-chain alkyl group on the aromatic nucleus. 12. The long-chain alkyl group has 4 to 2 carbon atoms.
The flame retardant according to claim 10 or 11, which is 0. 13. A compound having a structure in which an epoxy group of a halogenated epoxy resin is blocked with a monovalent carboxylic acid compound having a halogen atom and a long-chain alkyl group in its molecular structure, and an epoxy of a halogenated epoxy resin. The group is melt-kneaded with a compound having a structure blocked with a halogenated phenol, and the compound is melt-kneaded.
Flame retardant as described.