JPH08269341A - Flame retardant thermoplastic resin composition and flame retardant agent - Google Patents

Abstract

PURPOSE: To obtain a flame retardant thermoplastic resin composition containing a thermoplastic resin and a compound having a structure in which an epoxy group of a halogenated epoxy resin is blocked by an imide compound containing a halogen atom, excellent in light and heat resistances, and useful for electric or electronic parts, etc. CONSTITUTION: This flame retardant thermoplastic resin composition contains (A) a thermoplastic resin such as a styrene-based resin or a polymer alloy, etc., containing a styrene-based resin as one component and (B) a compound having a structure in which an epoxy group of a halogenated epoxy compound such as a halogenated bisphenol-type epoxy resin, etc., is blocked by an imide compound containing a halogen atom such as a halogenated aromatic imide. Furthermore, a blending ratio of the components A to B is preferably 1-50 pts.wt. component B based on 100 pts.wt. component A.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame-retardant thermoplastic resin composition which is excellent in thermal stability, light resistance and flame retardancy during molding, and a flame retardant which imparts these characteristics to the thermoplastic resin. Regarding

[0002]

2. Description of the Related Art In recent years, as a flame retardant for a thermoplastic resin composition, a halogenated bisphenol A type epoxy resin or an epoxy group of a halogenated bisphenol A type epoxy resin has a tribromophenol or the like because of its good flame retardant effect. Compounds having a structure blocked with halogenated phenols are widely used.However, since these compounds are prone to discoloration or yellowing due to photooxidation deterioration by ultraviolet rays, the light resistance of molded products is extremely poor. It was

Therefore, conventionally, Japanese Patent Laid-Open No. 4-345665 has been proposed.
The publication discloses a technique using a compound having a structure in which a terminal epoxy group of a halogenated epoxy resin is reacted with benzophenone or salicylic acid as a flame retardant for a thermoplastic resin.

[0004]

However, the above-mentioned Japanese Unexamined Patent Application Publication No.
When the compound described in JP-A-345665 is used as a flame retardant for a thermoplastic resin, an effect of improving light resistance is recognized, but it is not yet at a sufficient level, and when kneading by an extruder or molding by an injection molding machine. The heat history in the molten state causes the thermal decomposition of halogenated epoxy resin and the polymerization reaction of the epoxy group, resulting in discoloration of the molded product, and the deterioration of the resin flowability and the occurrence of gelled foreign matter during molding processing. There was a problem of impairing thermal stability.

The problem to be solved by the present invention is to provide a flame-retardant thermoplastic resin composition and a thermoplastic resin which are remarkably excellent in light resistance of a molded article and have improved thermal stability during molding. On the other hand, it is to provide a flame retardant capable of imparting the above properties.

[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, a structure in which the epoxy group of a halogenated epoxy resin is blocked with a halogen atom-containing amide compound is proposed. A compound that has, or
By using a compound that has a structure in which the epoxy group of the epoxy resin is blocked with a halogen atom-containing imide compound and a halogen-based flame retardant in combination, the light resistance of the thermoplastic resin molded product can be significantly improved and the thermal stability is improved. It was found that the above can be improved, and the present invention has been completed.

That is, the present invention comprises a thermoplastic resin (A),
A flame-retardant thermoplastic resin composition and a thermoplastic resin (A), characterized in that the epoxy group of the halogenated epoxy resin contains a compound (B) having a structure blocked with a halogen atom-containing imide compound. , A flame-retardant thermoplastic resin characterized by comprising a compound (B1) having a structure in which an epoxy group of an epoxy resin is blocked with a halogen atom-containing imide compound and a halogen-based organic flame retardant (B2) as essential components. Resin composition, epoxy group of halogenated epoxy resin, a flame retardant characterized by containing a compound having a structure blocked with a halogen atom-containing imide compound, and epoxy group of the epoxy resin, halogen atom-containing imide The present invention relates to a flame retardant comprising a compound having a structure blocked with a compound and a halogen-based organic flame retardant as essential components.

The flame retardant of the present invention is a compound (B) having a structure in which the epoxy group of the halogenated epoxy resin is blocked with a halogen atom-containing imide compound as described above, and
The epoxy group of the epoxy resin is a mixture of a compound (B1) having a structure blocked with a halogen atom-containing imide compound and a halogen-based organic flame retardant (B2), but from the viewpoint of flame retardant effect as a flame retardant. The former compound (B) is particularly preferable.

The halogenated epoxy resin which can be used in the compound (B) 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 and halogenated resorcinol. Type epoxy resin, halogenated hydroquinone type epoxy resin, halogenated bisphenol A novolak type epoxy resin, halogenated methylresorcinol type epoxy resin, halogenated resorcinol novolak type epoxy resin, etc., but usually an average degree of polymerization of 0 to 50. The halogenated bisphenol type epoxy resin of is used.

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.

In the present invention, the halogen atom-containing imide compound to be reacted with the above-mentioned epoxy resin is an essential component which imparts the effects of light resistance and heat stability to the halogenated epoxy resin.

The halogen atom-containing imide compound is not particularly limited, and examples thereof include dibromosuccinimide, tribromoglutarimide, monobromosuccinimide, dibromoglutarimide, monobromoglutarimide, dichlorosuccinimide, trichloroglutarimide, Halogenated aliphatic imides such as monochlorosuccinimide, dichloroglutarimide, and monochloroglutarimide, or phthalimide, 1,8-naphthalenedicarboximide, 1,9-anthracenedicarboximide, 1,10-phenanthrenecarboximide, 3 , 4-fluoranthene dicarboximide, 1,
Examples thereof include halogenated aromatic imides having a halogen atom at any position on the aromatic ring of aromatic imide such as 12-chrysene dicarboximide and 1,14-pentacene dicarboximide. Among them, the latter halogenated aroma Group imides are preferable from the viewpoint of light resistance and heat resistance, and tetrabromophthalimide is particularly preferable from the viewpoint that these effects are remarkable.

The compound having a structure in which the epoxy group in the above halogenated epoxy resin is blocked with a halogen atom-containing imide compound is further processed by using a halogenated dicarboxylic acid monometal salt together with a halogenated phenol. The thermal stability over time can be improved.

Examples of the halogenated phenols used here include dibromophenol, dibromocresol, tribromophenol, pentabromophenol,
Dichlorophenol, dichlorocresol, trichlorocresol, pentachlorophenol and the like,
Of these, tribromophenol and pentabromophenol are preferable because they have excellent flame retardancy.

Examples of the compound having a structure in which the epoxy group in the halogenated epoxy resin is blocked with a halogen atom-containing imide compound include those represented by the following general formula.

General formula 1

[0017]

Embedded image

(In the general formula 1, R is a methylene group, 2,2-
A propylidene group and a phenylmethyl group are shown, and X is a bromine atom and a chlorine atom. Y ₁ and Y ₂ independently represent a structural formula represented by the following general formula 2 or general formula 3, but Y ₁ and Y ₂ do not become general formula 3 at the same time. Also, n is 0 to 5
0 is an integer, and m is an integer of 1 to 4. )

General formula 2

[0020]

Embedded image

(In the general formula 2, M represents an aromatic hydrocarbon group or a cycloaliphatic hydrocarbon group, and X represents a bromine atom or a chlorine atom substituting on the aromatic hydrocarbon group or the cycloaliphatic hydrocarbon group. And 1 represents the number that can be substituted on the hydrocarbon group represented by M.)

General formula 3

[0023]

Embedded image

(In the general formula 3, X represents a bromine atom or a chlorine atom, and o represents an integer of 1 to 3.)

The compound (B) having a structure in which the epoxy group of the halogenated epoxy resin is blocked by a halogen atom-containing imide compound, which is the flame retardant of the present invention, can be produced by various methods. A method in which a halogenated bisphenol is reacted to give a high molecular weight and then a halogen atom-containing imide compound is heated to react, or a halogenated epoxy resin is heated to react with a halogenated bisphenol and a brominated aromatic imide, or a halogenated bisphenol is used. , A halogenated phenol and a halogen atom-containing imide compound are reacted by heating.

When the halogenated bisphenol type epoxy resin is used as the halogenated epoxy resin by the above method and the above method, specifically, it can be produced by the following method.

That is, a halogenated bisphenol type epoxy resin is obtained by a condensation reaction between a halogenated bisphenol and epichlorohydrin or an addition reaction between a diglycidyl ether of a halogenated bisphenol obtained by the condensation reaction and a halogenated bisphenol, and further a halogen atom. A diglycidyl ether of a halogenated bisphenol is obtained by a method of heating the contained imide compound at 100 to 230 ° C. in the presence or absence of a catalyst, or by a condensation reaction of a halogenated bisphenol and epichlorohydrin, and halogenating the glycidyl ether. The target halogenated bisphenol flame retardant can be obtained by a method of reacting bisphenol and an imide compound containing a halogen atom by heating at 100 to 230 ° C. in the presence or absence of a catalyst.

Examples of the catalyst include alkali metal hydroxides such as sodium hydroxide, tertiary amines such as dimethylbenzylamine, imidazoles such as 2-ethyl-4methylimidazole, and quaternary amines such as tetramethylammonium chloride. Ammonium salts, phosphonium salts such as ethyltriphenylphosphonium iodide, phosphines such as triphenylphosphine, and the like can be used. The reaction solvent is not particularly necessary and may not be used.

In the above and other methods, when the halogen atom-containing imide compound is reacted by heating,
The halogen atom-containing imide compound and a sealing agent such as halogenated phenols may be used in combination.

The amount of the halogen atom-containing imide compound used is not particularly limited, but it is preferable that the number of functional groups of the imide group is equal to or smaller than the number of functional groups of the residual epoxy group of the halogenated epoxy resin. It is preferable to use the epoxy resin and the halogen atom-containing imide compound in a content ratio of 0.01 to 10% by weight based on the total amount, from the viewpoint of thermal stability and heat distortion temperature during molding.

As described above, in the present invention, not only the above-mentioned flame retardants but also the compound (B1) having a structure in which the epoxy group of the epoxy resin is blocked with a halogen atom-containing imide compound, and a halogen compound Flame retardant (B
A mixture containing 2) and 2 as essential components can be used.

The epoxy resin used in the compound (B1) is not particularly limited, and examples thereof include bisphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, resorcin type epoxy resin, hydroquinone type epoxy resin, bisphenol A. Examples thereof include novolac type epoxy resin, methylresorcin type epoxy resin, and resorcin novolac type epoxy resin, and bisphenol type epoxy resin having an average degree of polymerization of 0 to 50 is usually used.

Specific examples of the bisphenol constituting the bisphenol type epoxy resin include bisphenol A, bisphenol F, bisphenol S and the like.

In the compound (B1), as the halogen atom-containing imide compound to be reacted with the above-mentioned epoxy resin, any of those mentioned in the above compound (B) can be used. Among them, halogenated aromatic imides have light resistance and From the viewpoint of heat resistance, tetrabromophthalimide is particularly preferable.

Further, the method for producing the compound (B1) is not particularly limited, and the epoxy resin and the halogen atom-containing imide compound may be used in the presence of a catalyst or without a catalyst.
A method of heating and reacting at 00 to 230 ° C. may be mentioned,
In particular, when a bisphenol type epoxy resin is used, it can be specifically manufactured by the following method.

That is, a bisphenol type epoxy resin is obtained by a condensation reaction between bisphenol and epichlorohydrin or an addition reaction between bisphenol diglycidyl ether obtained by the condensation reaction and bisphenol, and a halogen atom-containing imide compound in the presence of a catalyst. Alternatively, a method of reacting by heating at 100 to 230 ° C. in the absence of a catalyst, a condensation reaction of bisphenol and epichlorohydrin, or a diglycidyl ether of bisphenol obtained by the condensation reaction, bisphenol, and a halogen atom-containing imide compound are present in the presence of a catalyst. A diglycidyl ether of bisphenol is obtained by heating at 100 to 230 ° C. under a low temperature or without a catalyst, or a condensation reaction of bisphenol and epichlorohydrin, and the glycidyl ether is converted into bisphenol. 100 The cyclohexanol and halogen atom-containing imide compound in the presence of a catalyst or in the absence of catalyst
Examples thereof include a method of heating and reacting at 230 ° C.

Examples of the catalyst include alkali metal hydroxides such as sodium hydroxide, tertiary amines such as dimethylbenzylamine, imidazoles such as 2-ethyl-4methylimidazole, and quaternary amines such as tetramethylammonium chloride. Ammonium salts, phosphonium salts such as ethyltriphenylphosphonium iodide, phosphines such as triphenylphosphine, and the like can be used. The reaction solvent is not particularly necessary and may not be used.

Further, in the above production method, when the halogen atom-containing imide compound is heated and reacted, the halogen atom-containing imide compound and the halogenated phenol may be used in combination.

The halogen-based flame retardant used as the compound (B2) is not particularly limited. For example, the halogenated epoxy resin is not particularly limited. For example, a halogenated bisphenol type epoxy resin. , Halogenated phenol novolac type epoxy resin, halogenated cresol novolac type epoxy resin,
Halogenated resorcin-type epoxy resin, halogenated hydroquinone-type epoxy resin, halogenated bisphenol A novolac-type epoxy resin, halogenated methylresorcin-type epoxy resin, halogenated resorcin-novolak-type epoxy resin, and other halogenated epoxy resins, or halogenated versions thereof. Examples thereof include compounds having a structure in which the epoxy group of the epoxy resin is blocked with halogenated phenols.

The above-mentioned compound (B1) and flame retardant (B2)
Means that any combination of the above-exemplified compounds can be used. Among them, a compound obtained by blocking the terminal epoxy group of a bisphenol type epoxy resin with a halogen atom-containing imide compound as the compound (B1) from the viewpoint that the effect of the present invention is remarkable. It is preferable to use a compound having a structure in which the terminal epoxy group of a halogenated bisphenol type epoxy resin is blocked with a compound blocked with a halogenated phenol as the flame retardant (B2).

Further, the compound (B1) and the flame retardant (B
The method of using 2) is not particularly limited and may be independently added to the thermoplastic resin (A) described below, or after dry blending the compound (B1) and the flame retardant (B2), It may be added to the thermoplastic resin (A), or the compound (B1) and the flame retardant (B2) may be melt-kneaded and pelletized to be added to the thermoplastic resin (A). Above all, the compound (B1) and the flame retardant (B2) are melt-kneaded and pelletized and added to the thermoplastic resin (A) because the dispersibility in the thermoplastic resin (A) is extremely good. The method is preferred.

As a method for melt-kneading the above mixture and pelletizing it, for example, the epoxy group of the epoxy resin is
The temperature at which both the compound (B1) having a structure blocked with a halogen atom-containing imide compound and the halogen-based flame retardant (B2) melt, for example, 120 ° C to 230 ° C.
Examples of the method include a method in which the mixture is heated and melted and mixed, and the mixture may be any of various mixers that can be heated. Normally,
It is produced by a method of heating and stirring for about 15 minutes to 3 hours in a container having a stirring blade, but a Banbury mixer, an extruder or the like can be used if necessary.

The amount of the compound (B1) having a structure blocked with the halogen atom-containing imide compound in the mixture is not particularly limited, but the amount of the halogen atom-containing imide compound used is based on the total amount of these compounds. Is 0.01-
It is preferable to use it in the range of 10% by weight from the viewpoint of the releasability to metal, the thermal stability during molding, and the heat distortion temperature of the molded product.

The amount of the halogen atom-containing imide compound used may be in the range of more than 10% by weight, but in this case, improvement of the effect cannot be expected.

The thermoplastic resin 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 resins such as styrene copolymer (AAS resin) and acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin), polyolefin resins such as polyethylene and polypropylene, polybutylene terephthalate (PBT resin), polyethylene terephthalate (PET) Resins such as polyester resin, polycarbonate resin, polyamide resin, polyphenylene oxide (PPO) resin, alloy of PPO resin and polystyrene, ABS resin and polycarbonate resin , Alloys of ABS resins and PBT resins, alloy of polycarbonate resin and polyester resin, thermoplastic resin alloys such as polycarbonate resin and polyamide resins.

The flame retardant of the present invention can be applied not only to the above-mentioned thermoplastic resins but also to thermosetting resins such as epoxy resins, phenol resins and polyurethane resins. The blending amount of the flame retardant of the present invention with respect to these thermoplastic resins is not particularly limited, but is usually 1 to 50 parts by weight with respect to 100 parts by weight of the thermoplastic resin, among which the flame retardant effect is high and The amount is preferably 5 to 30 parts by weight from the viewpoint that physical properties such as impact resistance are less deteriorated.

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

The blending amount of these flame retardant aids (C) 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. From the point of view, 1 to 15 parts by weight is preferable.

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.

The resin composition of the present invention contains other flame retardants such as brominated flame retardants within a range that does not significantly impair the thermal stability during molding and the releasability from the mold during injection molding. Chlorine-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, inorganic flame retardants, etc. may be added, and if necessary, ultraviolet absorbers, light stabilizers, release agents, lubricants, colorants, plasticizers. Agents, fillers, foaming agents, impact resistance improvers, compatibilizers, coupling agents, heat stabilizers, antioxidants, reinforcing materials such as glass fibers, carbon fibers and aramid fibers can be added.

[0051]

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 the value expressed in eq / g. (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) Limit Injection Molding Test (Thermal Stability) The thermal stability was evaluated by putting the flame-retardant resin composition in an injection molding machine and repeating the injection molding to obtain discoloration and foreign matter in the appearance of the obtained molded product. This was done by measuring the number of injection moldings until contamination was observed. Specifically, a well-dried pellet of the flame-retardant resin composition was put into a 5 ounce injection molding machine equipped with a mold capable of molding a disk-shaped molded product (outer diameter 100 mm × thickness 3 mm) from a hopper. Injection molding is repeated, and the appearance of the obtained molded product is observed visually and with a magnifying glass (× 10) to determine the limit number of injection moldings until discoloration and contamination with foreign matter occur continuously. The sex was evaluated. (The higher the limit injection molding frequency, the better the thermal stability.)

The discoloration referred to in this test means the case where the surface of the molded product is entirely colored in brown. In addition, the term "contamination of foreign matter" means that a foreign matter of 1.0 mm2 or more is present on one surface of the molded product.
The case where there are more than one is shown. The stability was evaluated according to the following ranks.

Judgment Limit injection molding number ○: 200 times or more, practically no problem Δ: 100 to less than 200 times, practically difficult ×: Less than 100 times, practically mass production not possible

The molding conditions are as follows. Cylinder temperature: ABS, HIPS, ABS / PC
In the case of the polymer alloy of 250 ° C., PBT, in the case of the polymer alloy of PBT / PC, it is 270
℃

Injection pressure: 1400 to 500 kgf / cm 2 Mold temperature: 60 to 80 ° C. Injection time / cooling time: 10 seconds / 20 seconds

(7) Light resistance A test was performed with an Atlas Ci35A Weatherometer (manufactured by Toyo Seiki Co., Ltd.) for 100 hours, and the change in appearance of the test piece before and after the test was measured using a color difference meter. The test was conducted under the following conditions.

Irradiance: 0.30 W / m ² (at 340 nm) Black panel temperature: 55 ° C. Rainfall: None Inner filter. Glass: borosilicate outer filter. Glass: Soda lime Next, the flame retardant used in the present invention and the flame retardant to be compared were produced by Examples 1 to 4 and Comparative Examples 1 to 6.

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,
223.2 g (abbreviated as TBA) was placed in a 2 liter flask equipped with a water-cooled condenser, a thermometer and a stirrer, the inside was replaced with nitrogen gas, and the contents were heated and melted to 100 ° C.
After adding 0.3 g of a 10% aqueous solution of potassium hydroxide at
The reaction was carried out at 140 to 180 ° C for 5 hours.

The epoxy group content of the content is 1.23 ×
It was 10 ⁻³ eq / g. After the reaction, 1000 g of methyl isobutyl ketone was gradually added and the temperature was lowered to 80 ° C. to dissolve the contents. Further, 114 g of concentrated hydrochloric acid was added over about 30 minutes. The reaction was continued for another 3 hours, and it was confirmed by pH test paper that the reaction solution was neutral.

Next, potassium carbonate 120 g, the tetrabromophthalimide 528.0g addition, the temperature was raised to 120 ° C., was refluxed for 6 hours, 1000 cm ³ and the reaction mixture
Washed 3 times with water.

After washing, the reaction mixture was charged into a vacuum distillation apparatus, and water in the reaction solution was first distilled off under normal pressure, and then the temperature of the flask was raised to 160 ° C. and the pressure was reduced (maximum 1 torr), and the contents of the flask were removed. MIBK was distilled off. After distillation under reduced pressure,
The pressure was returned to normal pressure with nitrogen gas, 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 A. The property values of this flame retardant are shown in Table 1.

Example 2 720.0 g of EPICLON 152 and TBA149.
7 g and tribromophenol (abbreviated as TBP below) 33
4.0 g, 1.3 g of a 10% aqueous solution of sodium hydroxide, 26 g of concentrated hydrochloric acid, 27 g of potassium carbonate and 120.0 g of tetrabromophthalimide were used, except that
Flame retardant powder was obtained in the same manner as in Example 1. 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 TBA223.
2 g, TBP 167.0 g, concentrated hydrochloric acid 70 g, potassium carbonate 74 g, and tetrabromophthalimide 324.0 g
Flame retardant powder was obtained in the same manner as in Example 1 except that was changed to. This is designated as flame retardant C. The property values of this flame retardant are shown in Table 1.

Example 4 Diglycidyl ether of bisphenol A [EPICLON850 manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 189 g / eq] 189.0 g and bisphenol A
(Hereinafter abbreviated as BPA) 31.5g and TBP219.0g
Flame retardant powder d1 was obtained in the same manner as in Example 1 except that 17 g of concentrated hydrochloric acid, 19 g of potassium carbonate and 72.5 g of tetrabromophthalimide were used and the reaction was performed at 120 to 180 ° C. for 12 hours. .

Epiclon 152 360.0 g and T
Flame retardant powder d2 was obtained in the same manner as in Example 1 except that 111.6 g of BA and 0.2 g of a 10% aqueous solution of sodium hydroxide were used.

The flame retardant powder d1 and the flame retardant powder d2 were melt-mixed in a nitrogen atmosphere at 150 to 180 ° C. for 2 hours. The molten mixture was poured into a stainless pan, cooled and then pulverized to obtain a pale yellow flame retardant powder. This is designated as flame retardant D. The property values of this flame retardant are shown in Table 1.

Comparative Example 1 EPICLON 152 720.0 g and TBA 149.
7g and 2,4-dihydroxybenzophenone 63.5g
Was placed in a 2 liter flask equipped with a water-cooled condenser, thermometer, and stirrer, the inside was replaced with nitrogen gas, the contents were heated and melted, and 10% of sodium hydroxide was added at 100 ° C.
After adding 1.3 g of the aqueous solution, the mixture was reacted at 150 to 230 ° C. for 12 hours. After the reaction, it was poured into a stainless steel pan, cooled, and then pulverized to obtain a pale yellow flame retardant powder. This is designated as flame retardant E. The property values of this flame retardant are shown in Table 2.

Comparative Example 2 EPICLON 152 (720.0 g) and TBA223.
2 g and 2,4-dihydroxybebenzophenone 49.6
flame retardant powder was obtained in the same manner as in Comparative Example 1 except that the reaction was carried out at 150 to 230 ° C. for 12 hours using g and 0.2 g of a 10% aqueous solution of sodium hydroxide. This is designated as flame retardant F. The property values of this flame retardant are shown in Table 2.

Comparative Example 3 720.0 g of EPICLON 152 and TBP467.
0 g, salicylic acid 63.0 g and sodium hydroxide 10
% Aqueous solution 1.3 g and 12 at 150-230 ° C.
A flame retardant powder was obtained in the same manner as in Comparative Example 1 except that the reaction was performed for a time. This is designated as flame retardant G. The property values of this flame retardant are shown in Table 2.

[0072]

[Table 1]

[0073]

[Table 2]

Examples 5 to 13 and Comparative Examples 4 to 8 The respective components were blended in the compositions shown in Tables 2 to 4 and premixed with a tumbler mixer, and then a 30 mmφ twin-screw extruder (cylinder temperature: ABS 220-230 ° C for resin and HIPS resin, 240-250 ° C for polymer alloy of ABS resin and PC resin, 2 for PBT resin
Pelletized by setting 40-250 ° C).

Then, a 5 ounce injection molding machine (cylinder temperature is 230 ° C. for ABS resin and HIPS resin,
250 in the case of polymer alloy of ABS resin and PC resin
℃, in the case of PBT resin, set to 250 ℃) to prepare a test piece.

Using this test piece, the heat distortion temperature, Izod impact strength, flammability, light resistance and the like were measured. The results are shown in Tables 2 to 4. A limit injection molding test was conducted using a 5 ounce injection molding machine to evaluate thermal stability. The results are shown in Tables 2 and 4.

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 "Sebian 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 ".

[0079]

[Table 3]

[0080]

[Table 4]

[0081]

[Table 5]

[0082]

EFFECTS OF THE INVENTION According to the present invention, a flame-retardant thermoplastic resin composition having remarkably excellent light resistance of a molded article and improved thermal stability during molding and a thermoplastic resin are provided. A flame retardant capable of imparting the above properties can be provided.

That is, with the composition of the present invention, a flame-retardant molded product having excellent light resistance can be obtained.
It is useful as a material for automobiles. However, since the flame-retardant thermoplastic resin composition of the present invention is excellent in thermal stability during molding, productivity is improved.

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Claims (16)

[Claims] 1. A flame-retardant material comprising a thermoplastic resin (A) and a compound (B) having a structure in which an epoxy group of a halogenated epoxy resin is blocked with a halogen atom-containing imide compound. Thermoplastic resin composition. 2. The composition according to claim 1, wherein the compound (B) has a structure in which the epoxy group of the halogenated epoxy resin is blocked with a halogenated aromatic imide. 3. The composition according to claim 2, wherein the compound (B) is a compound having a structure in which an epoxy group of a halogenated bisphenol type epoxy resin is blocked with a halogen atom-containing imide compound. 4. The composition according to claim 3, wherein the compound (B) is a compound having a structure in which an epoxy group of a halogenated epoxy resin is blocked with a halogen atom-containing imide compound and a halogenated phenol. 5. An essential component comprising a thermoplastic resin (A), a compound (B1) having a structure in which an epoxy group of an epoxy resin is blocked with a halogen atom-containing imide compound, and a halogen-based organic flame retardant (B2). And a flame-retardant thermoplastic resin composition. 6. The composition according to claim 5, wherein the compound (B1) has a structure in which the epoxy group of the epoxy resin is blocked with a halogenated aromatic imide. 7. The compound (B1) has a structure in which the epoxy group of a bisphenol type epoxy resin is blocked with a halogenated aromatic imide, and the halogen-based organic flame retardant (B2) is a halogen. A composition according to claim 6, which is a bisphenol type epoxy resin flame retardant. 8. 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. . 9. 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. . 10. The flame-retardant thermoplastic resin composition according to claim 1, further comprising a flame retardant aid (D). 11. A flame retardant characterized by containing a compound having a structure in which an epoxy group of a halogenated epoxy resin is blocked with a halogen atom-containing imide compound. 12. The flame retardant according to claim 11, wherein the halogen atom-containing imide compound is a halogenated aromatic imide. 13. A compound having a structure in which an epoxy group of a halogenated epoxy resin is blocked with a halogen atom-containing imide compound, and an epoxy group of a halogenated bisphenol epoxy resin is a halogen atom-containing imide compound and a halogenated phenol. The flame retardant according to claim 11 or 12, which has a structure blocked with. 14. A flame retardant comprising a compound having a structure in which an epoxy group of an epoxy resin is blocked with a halogen atom-containing imide compound, and a halogen-based organic flame retardant as essential components. 15. The flame retardant according to claim 14, wherein the halogen atom-containing imide compound is a halogenated aromatic imide. 16. A compound having a structure in which the epoxy group of a halogenated epoxy resin is blocked with a halogen atom-containing imide compound, wherein the epoxy group of the bisphenol type epoxy resin has a structure blocked with a halogenated aromatic imide. The flame retardant according to claim 15, wherein the halogen-based organic flame retardant is a halogenated bisphenol type epoxy resin-based flame retardant.