JPH04300968A - Flame-retardant synthetic resin composition and flame retardant - Google Patents

Abstract

PURPOSE:To provide a flame-retardant resin composition excellent in weather resistance and flame retardance when molded, and also to provide a flame retardant. CONSTITUTION:The composition comprises (A) 100 pts.wt. of a synthetic resin, preferably a thermoplastic resin, and (B) 1-50 pts.wt. of a flame-retardant agent consisting of a compound having a structure in which the epoxy groups of a halogenated epoxy resin are blocked with a phosphate ester having active hydrogen atoms (e.g. a hydrogen phosphate compound) or with both the phosphate ester having the active hydrogen atoms and a halogenated phenol.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant synthetic resin composition that has excellent thermal stability during molding, weather resistance and flame retardancy, and a flame retardant that imparts these properties to the synthetic resin.

0002

[Prior Art] Conventionally, flame retardation of synthetic resins such as styrene resins and polyester resins has been studied, for example, in Japanese Patent Laid-Open No. 5
0-27843 has low volatility, non-bleeding properties,
A technique for adding and blending a flame retardant made of a halogenated bisphenol A type epoxy resin with excellent heat resistance, etc. and, if necessary, a flame retardant aid such as antimony trioxide, is also disclosed in JP-A-62-4737. disclosed a technique in which the epoxy group of an epoxy resin is blocked and modified with a halogenated phenol such as tribromophenol as a flame retardant.

0003

[Problem to be solved by the invention] However,
The flame-retardant synthetic resin described in Publication No. 27843 causes thermal decomposition of the halogenated epoxy resin and polymerization reaction of the epoxy group due to thermal history in the molten state during kneading with an extruder and molding with an injection molding machine. In addition to causing discoloration of the molded product, there were problems in that the flowability of the resin decreased and the thermal stability during molding processing was impaired due to the generation of gelled foreign substances.

[0004]Although the flame retardant described in JP-A No. 62-4737 has improved these problems to some extent, if it is used at a high molding temperature of 220°C or higher or if it is left to stay in a molding machine, However, the thermal stability during molding is still not sufficient due to the discoloration of the molded product due to the discoloration of the flame retardant itself and the generation of burnt foreign matter. Weather resistance was significantly inferior to that of resin.

The problem to be solved by the present invention is to provide a synthetic resin composition that has good thermal stability without problems during molding such as discoloration of the synthetic resin composition, decreased flowability of the resin, and generation of gelled foreign matter.
Moreover, it is an object of the present invention to provide a flame retardant synthetic resin composition with excellent weather resistance and a flame retardant that can impart thermal stability, weather resistance, and flame retardant properties to the synthetic resin.

[0006]

[Means for Solving the Problems] The present inventors have conducted intensive research to solve the above problems, and as a result, have completed the present invention.

That is, the present invention provides (A) a synthetic resin and (B)
) A flame-retardant synthetic resin composition characterized by containing a compound having a structure in which some or all of the epoxy groups of a halogenated epoxy resin are blocked with a phosphoric acid ester compound having active hydrogen, and The present invention relates to a flame retardant comprising a compound having a structure in which a part or all of the epoxy groups of a halogenated epoxy resin are blocked with a phosphoric acid ester compound having active hydrogen.

The halogenated epoxy resin that can be used in the present invention is not particularly limited, and includes, for example, halogenated bisphenol type epoxy resin, halogenated phenol novolak type epoxy resin, halogenated cresol novolak type epoxy resin, and halogenated resorcin type epoxy resin. resin, halogenated hydroquinone type epoxy resin, halogenated bisphenol A novolak type epoxy resin, halogenated methylresorcinol type epoxy resin, halogenated resorcinol type epoxy resin, halogenated resorcinol novolac type epoxy resin, etc., but usually halogen with an average degree of polymerization of about 0 to 50. Uses bisphenol-based epoxy resin.

Specific examples of halogenated bisphenols constituting this halogenated bisphenol type epoxy resin include dibromobisphenol A, tetrabromobisphenol A, dichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, tetrabromobisphenol F, Examples include dichlorobisphenol F, tetrachlorobisphenol F, dibromobisphenol S, tetrabromobisphenol S, dichlorobisphenol S, and tetrachlorobisphenol S.

[0010] In the present invention, the phosphoric acid ester compound having active hydrogen imparts thermal stability, light stability and flame retardancy to the synthetic resin, and the active hydrogen in the molecule binds to the epoxy resin of the halogenated epoxy resin. It is an essential component that reacts with groups and can be effectively included in the skeleton of halogenated epoxy resins.

Examples of such phosphoric acid ester compounds having active hydrogen include dimethyl hydrogen phosphite, diethyl hydrogen phosphite, diisopropyl hydrogen phosphite, dilauryl hydrogen phosphite, and diphenyl hydrogen phosphite. Hydrogen phosphite-based compounds such as phite, dinonylphenyl hydrogen phosphite, phosphonic acid-based compounds such as methylphosphonic acid, ethylphosphonic acid, isopropylphosphonic acid, butylphosphonic acid, phenylphosphonic acid, nonylphenylphosphonic acid, dimethylphosphine acids, phosphinic acid compounds such as diethylphosphinic acid, diisopropylphosphinic acid, dilaurylphosphinic acid, diphenylphosphinic acid, dinonylphenylphosphinic acid, and 9,10-dihydro-9-oxa-
10-phosphaphenanthrene-10-oxide, 1
0-deroxy-9,10-dihydro-9-oxa-10
-Phosphaphenanthrene, 6,8-dichloro-10-
10-phenoxy-9,10-dihydro-9-oxer
10-phosphaphenanthrene, 10-(3,5-di-
Examples include t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene compounds.

In the present invention, a halogenated phenol compound can be used in combination with the above-mentioned active hydrogen-containing phosphoric acid ester compound as a blocking compound capable of reacting with the epoxy group of the halogenated epoxy resin.

Specific examples of the halogenated phenol compounds include dibromophenol, dibromocresol, tribromophenol, pentabromophenol, dichlorophenol, dichlorocresol, trichlorophenol, and pentachlorophenol.

[0014] The compound of the present invention having a structure in which the epoxy group of a halogenated epoxy resin is capped with a phosphoric acid ester compound having active hydrogen, for example, a halogenated bisphenol compound, can be produced by the following method. can.

That is, a halogenated bisphenol type epoxy resin having an epoxy group is obtained by a condensation reaction between a halogenated bisphenol and epichlorohydrin, or an addition reaction between a diglycidyl ether of a halogenated bisphenol and a halogenated bisphenol, and further the epoxy resin The desired compound can be obtained by heating and reacting a phosphoric acid ester compound having active hydrogen at 100 to 230° C. in the presence of a catalyst or without a catalyst. At this time, a phosphoric acid ester compound having active hydrogen and a halogenated phenol compound may be used in combination.

There is no particular restriction on the amount of the phosphoric acid ester compound having active hydrogen, but the number of active hydrogens in the phosphoric acid ester compound is determined by the number of functional groups of the remaining epoxy groups of the halogenated epoxy resin. It can be used in the same number or less. Specifically, it can be used in an amount of 0.5 to 1 equivalent of the active hydrogen group of the phosphoric acid ester compound per equivalent of epoxy group of the halogenated epoxy resin, preferably 0.8 to 1.
1 equivalent.

Further, the phosphorus content of the obtained flame retardant is 0.
If the phosphorus content is less than 1% by weight, the coloring prevention effect and flame retardant effect tend to decrease, so it is desirable to use the phosphorus content so that the phosphorus content is 0.1% by weight or more.

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 hydroxides such as tetramethylammonium chloride. Phosphonium salts such as class ammonium salts, ethyltriphenylphosphonium iodide, and phosphines such as triphenylphosphine can be used. The reaction solvent is not particularly necessary and may not be used.

Examples of the synthetic resin (A) that can be used in the present invention include thermosetting resins such as epoxy resins, phenol resins, and polyurethane resins, polystyrene, rubber-modified polystyrene (HIPS resin), and acrylonitrile-styrene-butadiene. Polymers (ABS resin), styrenic resins such as acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin), polyolefin resins such as polyethylene and polypropylene,
Polyester resins such as polybutylene terephthalate (PBT resin) and polyethylene terephthalate (PET resin), polycarbonate resins, polyamide resins, polyphenylene oxide (PPO resins), and P
Thermoplastic resins include alloys of PO resin and polystyrene, alloys of ABS resins and polycarbonate resins, alloys of ABS resins and PBT resins, alloys of polycarbonate resins and polyester resins, alloys of polycarbonate resins and polyamide resins, and the like. Among these, thermoplastic resins can be particularly preferably used.

The blending amount of the flame retardant of the present invention in these synthetic resins is not particularly limited;
It is usually 1 to 50 parts by weight per 00 parts by weight, and 5 to 3 in terms of high flame retardant effect and little deterioration of physical properties such as impact resistance.
0 parts by weight is preferred.

The synthetic resin composition containing the synthetic resin and the flame retardant of the present invention may further contain antimony compounds such as antimony trioxide, antimony tetroxide, and antimony pentoxide, tin oxide, and tin hydroxide. tin-based compounds such as
By blending flame retardant aids such as molybdenum compounds such as molybdenum oxide and ammonium molybutate, zirconium compounds such as zirconium oxide and zirconium hydroxide, and boron compounds such as zinc borate and barium metaborate,
The flame retardant effect can be further enhanced.

[0022] The synthetic resin composition of the present invention is prepared by blending a predetermined amount of a synthetic resin, a flame retardant, and other additive components as necessary, and premixing the mixture with a mixer such as a Henschel mixer or a tumbler mixer. It can be easily produced by melt-kneading using an extruder, kneader, hot roll, Banbury mixer, etc.

[0023] The flame retardant synthetic resin composition of the present invention includes:
Other flame retardants may be added as long as they do not significantly impair thermal stability and weather resistance during molding, and if necessary, ultraviolet absorbers, light stabilizers, mold release agents, lubricants, colorants, and plasticizers may be added. agent, filler, foaming agent, heat stabilizer, glass fiber, carbon fiber,
Reinforcing materials such as aramid fibers can be added.

[0024]

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to these Examples.

[0025] All parts and percentages in the examples are based on weight, and evaluations in various tests are based on the following measurement methods. (1) Softening point test (ring and ball method) Measured in accordance with JIS K-2077. (2) Epoxy group content test The value is the reciprocal of the epoxy equivalent (g/eq) measured in accordance with JIS K-7236, expressed in eq/g units. (3) Hue (Gardner) test Powder sample 20.0±0.5 in a 100ml Erlenmeyer flask
Collect 20.0±0.5g of anisole (
Add sample 1st grade). Set a condenser in a flask, heat and dissolve, and after dissolving, cool to room temperature. Pour the sample solution into the Gardner tube up to the marked line, seal it, and compare it visually with the Gardner hue standard solution (JI) under diffused daylight.
SK-6901), and the hue is determined by the color number closest to that of the sample. (4) Heat coloring test Powder sample 20.0±0.5g was poured into an aluminum cup (outer diameter 10
0 mm x height 20 mm) and placed in a hot air dryer at 250±5°C and heated for 30 minutes.

Next, the sample after heating is cooled to room temperature, and the obtained sample is crushed. The hue of this sample is measured in the same manner as in (3) hue test, and this hue is taken as the value of the heat colorability test. (5) Heat deformation temperature test (load 18.6 kg/cm2) A
Measured according to STM D-648. (6) Izod impact strength test (notched) ASTM
Measurement was performed using a 1/4 inch thick test piece in accordance with D-256. (7) Flammability Test (UL-94) Underwriters Laboratories Subject 9
Based on method No. 4, length 5 inches x width 1/2 inch x
The measurement was performed using five test pieces each having a thickness of 1/8 inch. (8) Weather resistance test 10 on Sunshine Weatherometer (manufactured by Suga Test Instruments)
A 0-hour test was conducted, and changes in the appearance of the test piece before and after the test were measured using a color difference meter. (9) Molding machine retention test (thermal stability) Using a 5-ounce injection molding machine, the cylinder temperature was adjusted to ABS.
Molding was carried out at 230°C for resin and 270°C for PBT resin after residence time of 15 and 30 minutes,
The obtained disc-shaped molded product (outer diameter 100 mmφ x thickness 3 m
Visually observe the appearance of m) for discoloration and the presence of foreign matter,
Judgment was made according to the following ranks.

0027]◎…No discoloration○
… Slight yellow discoloration △ … Brown discoloration × … Severe discoloration and generation of many foreign substances Example 1 Diglycidyl ether of tetrabromobisphenol A (EPICLON152 manufactured by Dainippon Ink and Chemicals Co., Ltd.)
, epoxy equivalent 360g/eq, bromine content 48%)7
20.0g and tetrabromobisphenol A (hereinafter referred to as T
(abbreviated as BA) 150.0g and 9,10-dihydro-9-
Oxa-10-phosphaphenanthrene-10-oxide (HCA manufactured by Sanko Kagaku Co., Ltd., molecular weight 216, phosphorus content 14.2%, abbreviated as "HCA" in Table 1) 2
82.0g (0.9 active hydrogen groups per equivalent of epoxy group)
(equivalent equivalent) into a 1-liter separable flask equipped with a thermometer and a stirrer, and after purging the inside with nitrogen gas, the contents were heated and melted, and a 10% aqueous solution of sodium hydroxide was added at 100°C. After adding 2 g, the mixture was reacted at 150 to 180°C for 5 hours. After the reaction, the reaction product was poured into a stainless steel pan, cooled, and pulverized to obtain a pale yellow flame retardant powder. This material is referred to as flame retardant A. Further, the property values of this flame retardant are shown in Table 1.

Flame retardant A was blended with the composition shown in Table 2, premixed in a tumbler mixer, and then pelletized in a 30 mmφ twin screw extruder to obtain a flame retardant synthetic resin composition. Test specimens were then made using a 5 oz extruder.

[0029] The cylinder temperatures of the extruder and injection molding machine were set at 220 to 230°C. The test pieces were used to measure heat distortion temperature, Izod impact strength, flammability, etc., and the results are shown in Table 2. Further, the pelletized product was subjected to a retention test in a molding machine, and the results are shown in Table 2.

Example 2 Flame retardant A was blended in the composition shown in Table 2, premixed in a tumbler mixer, and then pelletized in a 30 mmφ twin screw extruder to obtain a flame retardant synthetic resin composition. Then 5
Test pieces were prepared using an ounce extruder.

[0031] The cylinder temperatures of the extruder and injection molding machine were set at 220 to 230°C. The test pieces were used to measure heat distortion temperature, Izod impact strength, flammability, etc., and the results are shown in Table 2. Further, the pelletized product was subjected to a retention test in a molding machine, and the results are shown in Table 2.

Example 3 EPICLON152 720.0g and TBA505
．． 0g and 25.0g of HCA (equivalent to 0.9 equivalents of active hydrogen group per equivalent of epoxy group) and 10g of sodium hydroxide.
% aqueous solution at 150-230°C.
A flame retardant powder was obtained in the same manner as in Example 1 except that the reaction time was changed. This material is designated as flame retardant B. Further, the property values of this flame retardant are shown in Table 1.

Flame retardant B was blended in the composition shown in Table 2, premixed using a tumbler mixer, and then pelletized using a 30 mmφ twin screw extruder to obtain a flame retardant synthetic resin composition. Test specimens were then made using a 5 oz extruder.

The cylinder temperatures of the extruder and injection molding machine were set at 220 to 230°C. The test pieces were used to measure heat distortion temperature, Izod impact strength, flammability, etc., and the results are shown in Table 2. Further, the pelletized product was subjected to a retention test in a molding machine, and the results are shown in Table 2.

Example 4 EPICLON152 720.0g and TBA150
．． 0g, 156.6g of HCA (equivalent to 0.5 equivalent of active hydrogen group per equivalent of epoxy group), and 1 of sodium hydroxide.
A flame retardant powder was obtained in the same manner as in Example 1, except that 0.2 g of a 0% aqueous solution was used. This material is designated as flame retardant C. Further, the property values of this flame retardant are shown in Table 1.

Flame retardant C was blended in the composition shown in Table 2, premixed in a tumbler mixer, and then pelletized in a 30 mmφ twin screw extruder to obtain a flame retardant synthetic resin composition. Test specimens were then made using a 5 oz extruder.

[0037] The cylinder temperatures of the extruder and injection molding machine were set at 220 to 230°C. The test pieces were used to measure heat distortion temperature, Izod impact strength, flammability, etc., and the results are shown in Table 2. In addition, the pelletized product was subjected to a retention test in a molding machine, and the results are shown in Table 2.

Example 5 EPICLON152 720.0g and TBA150
．． 0g and 2,4,6-tribromophenol (hereinafter TB
P), 135.0 g of HCA (equivalent to 0.9 equivalents of active hydrogen group per equivalent of epoxy group), and 1.0 g of a 10% aqueous solution of sodium hydroxide,
A flame retardant powder was obtained in the same manner as in Example 1, except that the reaction was carried out at 0 to 180°C for 12 hours. This material is designated as flame retardant D. Further, the property values of this flame retardant are shown in Table 1.

Flame retardant D was blended in the composition shown in Table 3, premixed in a tumbler mixer, and then pelletized in a 30 mmφ twin screw extruder to obtain a flame retardant synthetic resin composition. Test specimens were then made using a 5 oz extruder.

[0040] The cylinder temperatures of the extruder and injection molding machine were set at 220 to 230°C. The test pieces were used to measure heat distortion temperature, Izod impact strength, flammability, etc., and the results are shown in Table 3. In addition, the pelletized product was subjected to a retention test in a molding machine, and the results are shown in Table 3.

Example 6 EPICLON152 720.0g and TBA150
．． 0g and TBP220.0g and phenylphosphonic acid (molecular weight 158, phosphorus content 19.5%, in Table 1,
50.0 g (equivalent to 0.9 equivalent of active hydrogen group per equivalent of epoxy group) and 1 of sodium hydroxide.
1 at 150-180℃ using 1.0g of 0% aqueous solution.
A flame retardant powder was obtained in the same manner as in Example 1, except that the reaction was carried out for 2 hours. This material is designated as flame retardant E. Further, the property values of this flame retardant are shown in Table 1.

Flame retardant E was blended in the composition shown in Table 3, premixed in a tumbler mixer, and then pelletized in a 30 mmφ twin screw extruder to obtain a flame retardant synthetic resin composition. Test specimens were then made using a 5 oz extruder.

[0043] The cylinder temperatures of the extruder and injection molding machine were set at 220 to 230°C. The test pieces were used to measure heat distortion temperature, Izod impact strength, flammability, etc., and the results are shown in Table 3. In addition, the pelletized product was subjected to a retention test in a molding machine, and the results are shown in Table 3.

Example 7 EPICLON152 720.0g and TBA150
．． 0g, TBP287.0g, and dinonylphenyl hydrogen phosphite (molecular weight 486, phosphorus content 6.
4%, abbreviated as “DNPHP” in Table 1) 194.
0g (equivalent to 0.9 equivalents of active hydrogen group per equivalent of epoxy group) and 1.0g of a 10% aqueous solution of sodium hydroxide, except for changing to react at 150 to 180 ° C. for 12 hours. A flame retardant powder was obtained in the same manner as in Example 1. This material is designated as flame retardant F. Further, the property values of this flame retardant are shown in Table 1.

Flame retardant F was blended in the composition shown in Table 3, premixed in a tumbler mixer, and then pelletized in a 30 mmφ twin screw extruder to obtain a flame retardant synthetic resin composition. Test specimens were then made using a 5 oz extruder.

[0046] The cylinder temperatures of the extruder and injection molding machine were set at 220 to 230°C. The test pieces were used to measure heat distortion temperature, Izod impact strength, flammability, etc., and the results are shown in Table 3. In addition, the pelletized product was subjected to a retention test in a molding machine, and the results are shown in Table 3.

Example 8 EPICLON152 720.0g and TBA150
．． 0g, TBP220.0g and diphenylphosphinic acid (molecular weight 218, phosphorus content 14.1%, abbreviated as "DPP" in Table 1) 136.0g (equivalent to 0.9 equivalents of active hydrogen groups per equivalent of epoxy group) ) and 1.0 g of a 10% aqueous solution of sodium hydroxide.
Example 1 except that the reaction was carried out at ℃ for 12 hours.
A flame retardant powder was obtained in the same manner as above. This material is referred to as flame retardant G. Further, the property values of this flame retardant are shown in Table 1.

Flame retardant G was blended in the composition shown in Table 3, premixed using a tumbler mixer, and then pelletized using a 30 mmφ twin screw extruder to obtain a flame retardant synthetic resin composition. Test specimens were then made using a 5 oz extruder.

[0049] The cylinder temperatures of the extruder and injection molding machine were set at 220 to 230°C. The test pieces were used to measure heat distortion temperature, Izod impact strength, flammability, etc., and the results are shown in Table 3. In addition, the pelletized product was subjected to a retention test in a molding machine, and the results are shown in Table 3.

Example 9 Flame retardant A was blended in the composition shown in Table 4, premixed in a tumbler mixer, and then pelletized in a 30 mmφ twin screw extruder to obtain a flame retardant synthetic resin composition. Then 5
Test pieces were prepared using an ounce extruder.

[0051] The cylinder temperatures of the extruder and injection molding machine were set at 250 to 260°C. The test pieces were used to measure heat distortion temperature, Izod impact strength, flammability, etc., and the results are shown in Table 4. Further, the pelletized product was subjected to a retention test in a molding machine, and the results are shown in Table 4.

Example 10 Flame retardant A was blended in the composition shown in Table 4, premixed in a tumbler mixer, and then pelletized in a 30 mmφ twin screw extruder to obtain a flame retardant synthetic resin composition. Then 5
Test pieces were prepared using an ounce extruder.

[0053] The cylinder temperatures of the extruder and injection molding machine were set at 250 to 260°C. The test pieces were used to measure heat distortion temperature, Izod impact strength, flammability, etc., and the results are shown in Table 4. Further, the pelletized product was subjected to a retention test in a molding machine, and the results are shown in Table 4.

Example 11 Flame retardant B was blended in the composition shown in Table 4, premixed in a tumbler mixer, and then pelletized in a 30 mmφ twin screw extruder to obtain a flame retardant synthetic resin composition. Then 5
Test pieces were prepared using an ounce extruder.

[0055] The cylinder temperatures of the extruder and injection molding machine were set at 250 to 260°C. The test pieces were used to measure heat distortion temperature, Izod impact strength, flammability, etc., and the results are shown in Table 4. Further, the pelletized product was subjected to a retention test in a molding machine, and the results are shown in Table 4.

Comparative Example 1 EPICLON152 720.0g and TBA150
．． The mixture was placed in a 1 liter separable flask equipped with a thermometer and a stirrer, the inside was replaced with nitrogen gas, the contents were melted by heating, and 0.2 g of a 10% aqueous solution of sodium hydroxide was added at 100°C. After that, the mixture was reacted at 150 to 180°C for 5 hours. After the reaction, the reaction product was poured into a stainless steel pan, cooled, and pulverized to obtain a pale yellow flame retardant powder. This material is referred to as flame retardant H. Further, the property values of this flame retardant are shown in Table 1.

Flame retardant H was blended in the composition shown in Table 2, premixed in a tumbler mixer, and then pelletized in a 30 mmφ twin screw extruder to obtain a flame retardant synthetic resin composition. Test specimens were then made using a 5 oz extruder.

[0058] The cylinder temperatures of the extruder and injection molding machine were set at 220 to 230°C. The test pieces were used to measure heat distortion temperature, Izod impact strength, flammability, etc., and the results are shown in Table 2. Further, the pelletized product was subjected to a retention test in a molding machine, and the results are shown in Table 2.

Comparative Example 2 EPICLON152 720.0g, TBA150
．． 0g, TBP440.0 and 10 of sodium hydroxide
Comparative Example 1 except that 1.0 g of % aqueous solution was used.
A flame retardant powder was obtained in the same manner as above. This material is designated as flame retardant I. Further, the property values of this flame retardant are shown in Table 1.

Flame retardant I was blended with the composition shown in Table 3, premixed in a tumbler mixer, and then pelletized in a 30 mmφ twin screw extruder to obtain a flame retardant synthetic resin composition. Test specimens were then made using a 5 oz extruder.

[0061] The cylinder temperatures of the extruder and injection molding machine were set at 220 to 230°C. The test pieces were used to measure heat distortion temperature, Izod impact strength, flammability, etc., and the results are shown in Table 3. In addition, the pelletized product was subjected to a retention test in a molding machine, and the results are shown in Table 3.

Comparative Example 3 Flame retardant I was blended in the composition shown in Table 3, premixed in a tumbler mixer, and then pelletized in a 30 mmφ twin screw extruder to obtain a flame retardant synthetic resin composition. Then 5
Test pieces were prepared using an ounce extruder.

[0063] The cylinder temperature of the extruder and injection molding machine was set at 220 to 230°C. The test pieces were used to measure heat distortion temperature, Izod impact strength, flammability, etc., and the results are shown in Table 3. In addition, the pelletized product was subjected to a retention test in a molding machine, and the results are shown in Table 3.

Comparative Example 4 Flame retardant H was blended in the composition shown in Table 4, premixed in a tumbler mixer, and then pelletized in a 30 mmφ twin screw extruder to obtain a flame retardant synthetic resin composition. Then 5
Test pieces were prepared using an ounce extruder.

[0065] The cylinder temperatures of the extruder and injection molding machine were set at 250 to 260°C. The test pieces were used to measure heat distortion temperature, Izod impact strength, flammability, etc., and the results are shown in Table 4. Further, the pelletized product was subjected to a retention test in a molding machine, and the results are shown in Table 4.

Comparative Example 5 Flame retardant H was blended in the composition shown in Table 4, premixed in a tumbler mixer, and then pelletized in a 30 mmφ twin screw extruder to obtain a flame retardant synthetic resin composition. Then 5
Test pieces were prepared using an ounce extruder.

[0067] The cylinder temperatures of the extruder and injection molding machine were set at 250 to 260°C. The test pieces were used to measure heat distortion temperature, Izod impact strength, flammability, etc., and the results are shown in Table 4. Further, the pelletized product was subjected to a retention test in a molding machine, and the results are shown in Table 4.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

[Table 3]

[0071]

[Table 4]

(In Tables 1 to 4, the ABS resin is "Sevian V" manufactured by Daicel Chemical Co., Ltd., the PBT resin is "Barox" manufactured by Japan GE Plastics Co., Ltd., and the antimony trioxide is "Sebian V" manufactured by Nippon Seiko Co., Ltd. "ATOX-F" and glass fiber represent "Chopped Strad" manufactured by Nittobo.)

00
73]

[Effects of the Invention] The flame-retardant synthetic resin composition of the present invention has excellent thermal stability during molding processing, such as discoloration of the resin composition, generation of burnt foreign matter, decrease in flowability of the resin, and generation of gelled foreign matter. Since a molded product with a good appearance can be obtained and the weather resistance is extremely excellent, it is particularly useful as a housing material for office automation equipment and a material for electronic/electrical parts.

Furthermore, the flame retardant of the present invention does not itself cause discoloration at high temperatures, and may cause discoloration of the resin composition, generation of burnt foreign matter, decrease in flowability of the resin, generation of gelled foreign matter, etc. during molding processing. Thermal stability, weather resistance, and flame retardancy can be imparted to synthetic resins.

Claims (12)

[Claims] Claim 1: A flame retardant product comprising (A) a synthetic resin and (B) a compound having a structure in which the epoxy groups of a halogenated epoxy resin are blocked with a phosphoric acid ester compound having active hydrogen. synthetic resin composition. 2. The flame-retardant synthetic resin composition according to claim 1, wherein the synthetic resin (A) is a thermoplastic resin. 3. The flame retardant according to claim 1 or 2, wherein the compound (B) is a compound having a structure in which the epoxy group of a halogenated epoxy resin is blocked with a phosphoric acid ester compound having active hydrogen and a halogenated phenol. synthetic resin composition. 4. The flame-retardant synthetic resin composition according to claim 1, wherein the phosphoric acid ester compound having active hydrogen is a phosphonic acid compound or a phosphinic acid compound. 5. The flame-retardant synthetic resin composition according to claim 1, wherein the phosphoric acid ester compound having active hydrogen is a hydrogen phosphite compound. 6. Claims 1, 2, 3, wherein the phosphoric acid ester compound having active hydrogen is a 9,10-dihydro-9-oxa-10-phosphaphenanthrene compound.
5. The flame-retardant synthetic resin composition according to 4 or 5. 7. Compound (B) is a compound having a structure in which the epoxy group of a halogenated epoxy resin is blocked by a phosphoric acid ester compound having active hydrogen and a halogenated phenol compound. , 4, 5 or 6
The flame retardant synthetic resin composition described. 8. A flame retardant comprising a compound having a structure in which the epoxy groups of a halogenated epoxy resin are blocked with a phosphoric acid ester compound having active hydrogen. 9. The flame retardant according to claim 8, which comprises a compound having a structure in which the epoxy group of a halogenated epoxy resin is blocked with a phosphoric acid ester compound having active hydrogen and a halogenated phenol. 10. The flame retardant according to claim 8 or 9, wherein the phosphoric acid ester compound having active hydrogen is a phosphonic acid compound or a phosphinic acid compound. 11. The flame retardant according to claim 8, 9 or 10, wherein the phosphoric acid ester compound having active hydrogen is a hydrogen phosphite compound. 12. Claims 8, 9, 1, wherein the phosphoric acid ester compound having active hydrogen is a 9,10-dihydro-9-oxa-10-phosphaphenanthrene compound.
The flame retardant according to 0 or 11.