JPH05295277A - Flame retardant composition and flame retardant thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in impact resistance and useful for an electric equipment, etc., by melt-blending a halogenated epoxy resin-based flame-retardant with an inorganic flame-retardant assistant and a coupling agent. CONSTITUTION:The objective composition is obtained by melt-blending (A) a halogenated epoxy resin-based flame-retardant such as a halogenated bisphenol A type epoxy resin with (B) preferably 10 to 40wt.% [based on component (A)] inorganic flame retardant assistant such as anitmony oxide and/or (C) preferably 0.5 to 5wt.% coupling agent such as a silane coupling agent (e.g. vinyl triethoxysilane). In addition, a flame-retardant thermoplastic resin composition can be obtained by blending this composition with a thermoplastic resin such as PS.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Conventionally, as a flame retardant for a thermoplastic resin composition, for example, JP-A-50-27843 discloses a flame retardant composed of a halogenated epoxy resin, or JP-A-HEI-1.
JP-A-240571 discloses a flame retardant comprising a compound having a structure in which a terminal epoxy group of a halogenated epoxy resin is partially or wholly blocked with a halogenated phenol, and a flame retardant thermoplastic resin composition using the same. In each of the flame-retardant thermoplastic resin compositions, a technique is disclosed in which an inorganic flame-retardant auxiliary agent such as antimony trioxide is further used in order to enhance the flame-retardant effect.

When a flame retardant is used in combination with an inorganic flame retardant aid in the above prior art, first, the flame retardant, the thermoplastic resin and the inorganic flame retardant aid are first mixed with a tumbler mixer or a Henschel. The flame-retardant thermoplastic resin composition is obtained by dry blending with a mixer such as a mixer and then melt-mixing them with a kneading machine such as a Banbury mixer or an extruder.

[0004]

However, it comprises a flame retardant comprising the above conventional halogenated epoxy resin, or a compound having a structure in which a part or all of the terminal epoxy groups of the halogenated epoxy resin are blocked with a halogenated phenol. The technology of dry-blending a flame retardant, an inorganic flame retardant, and a thermoplastic resin, and further melt-mixing them has a problem that the falling weight impact strength showing impact resistance, particularly practical impact resistance, is inferior. Had.

On the other hand, when a flame-retardant thermoplastic resin composition is prepared by blending a flame-retardant agent and an inorganic flame-retardant auxiliary agent with a thermoplastic resin, the impact resistance of the flame-retardant thermoplastic resin composition obtained is improved. It is well known to add a coupling agent for the purpose of improvement. However, when the conventional halogenated epoxy resin-based flame retardant, the coupling agent, and the thermoplastic resin are dry blended and then melt-kneaded, the effect of improving impact resistance is not recognized at all.

The problem to be solved by the present invention is to provide a flame retardant composition which is remarkably excellent in impact resistance, particularly the effect of improving drop impact strength, and a flame retardant thermoplastic resin composition which is excellent in impact resistance. Especially.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventors of the present invention have previously melted an inorganic flame retardant auxiliary agent and / or a coupling agent into a halogenated epoxy resin flame retardant. The mixed composition becomes an excellent flame retardant with the above-mentioned drawbacks improved, and when it is added to a thermoplastic resin, it is impact resistant, and particularly, it has practical impact resistance. It was found that a thermosetting thermoplastic resin composition was obtained, and the present invention was completed.

That is, the present invention is characterized in that the halogenated epoxy resin flame retardant (A) and the inorganic flame retardant auxiliary (B) and / or the coupling agent (C) are melt-mixed. A flame retardant composition, a flame retardant composition (1) obtained by melt-mixing a halogenated epoxy resin flame retardant (A) with an inorganic flame retardant aid (B) and / or a coupling agent (C);
It relates to a flame-retardant thermoplastic resin composition containing a thermoplastic resin (2).

Examples of the halogenated epoxy resin-based flame retardant which can be used in the present invention include halogenated epoxy resins and compounds having a structure in which a part or all of terminal epoxy groups of the halogenated epoxy resin are blocked with halogenated phenol. Of these, halogenated epoxy resins are preferred because they have excellent light resistance when made into a flame-retardant thermoplastic resin composition.

Examples of the halogenated epoxy resin include 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 epoxy resin. Examples thereof include bisphenol A novolac type epoxy resin, halogenated methylresorcinol type epoxy resin, halogenated resorcinol novolac type epoxy resin and the like. Among them, halogenated bisphenol type epoxy resin is preferable from the viewpoint of excellent heat resistance and light resistance. Further, a halogenated bisphenol type epoxy resin having an average degree of polymerization of 0 to 100 is preferable because it has excellent compatibility with a thermoplastic resin when used as a flame retardant composition and improves impact resistance, and particularly, an average degree of polymerization of 0 to 20. The halogenated bisphenol type epoxy resin is preferable because it has a remarkably excellent effect of improving impact resistance.

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, Examples thereof include dichlorobisphenol F, tetrachlorobisphenol F, dibromobisphenol S, tetrabromobisphenol S, dichlorobisphenol S and tetrachlorobisphenol S.

Specific examples of halogenated phenols that can be used as a compound that blocks some or all of the terminal epoxy groups of the halogenated epoxy resin include dibromophenol, dibromocresol, tribromophenol, pentabromophenol, dichlorophenol, Examples thereof include dichlorocresol, trichlorophenol, pentachlorophenol, dibromobutylphenol, dibromoethylphenol, dibromopropylphenol and the like.

Examples of the inorganic flame retardant aids that can be used in the present invention include antimony oxides such as antimony trioxide, antimony tetraoxide and antimony pentoxide, tin compounds such as tin oxide and tin hydroxide, molybdenum oxide and molybdenum. Examples thereof include molybdenum-based compounds such as ammonium acidate, zirconium-based compounds such as zirconium oxide and zirconium hydroxide, and boron-based compounds such as zinc borate and barium metaborate. Among them, antimony oxide is preferable because it has a significantly improved flame retardancy.

Coupling agents usable in the present invention include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy).
Silane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2
-Aminoethyl) 3-aminopropylmethyldimethoxysilane, silane coupling agent such as 3-mercaptopropyltrimethoxysilane, isopropyltriisostearoyl titanate, isopropyl tris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctylphosphite) titanate Titanium coupling agents such as bis (dioctylpyrophosphate) oxyacetate titanate, isopropyl trioctanoyl titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, acetomethoxyaluminum diisopropylate, aceto Ethoxy aluminum diisopropylate, acetopropoxy aluminum diisopropylate, aceto Butoxy may be mentioned aluminum coupling agent diisopropylate. Among them, the silane coupling agent is preferable from the viewpoint of excellent impact resistance when the flame-retardant thermoplastic resin composition is used.

The flame retardant composition of the present invention is obtained by melting and mixing the above-mentioned halogenated epoxy resin flame retardant (A) and the inorganic flame retardant auxiliary (B) and / or coupling agent (C). Among them, the halogenated epoxy resin flame retardant (A), the inorganic flame retardant auxiliary (B), and the coupling agent (C) are particularly excellent in the impact resistance improving effect.
Those obtained by melt-mixing and are preferable.

The melt mixing referred to in the present invention is not only the melt mixing of (A) and (B) and / or (C) as described below, but also of (B) and / or (C). It also includes the case of synthesizing (A) in the presence or the case of adding (B) and / or (C) to the reaction system during the synthetic reaction of (A).

Next, the method for producing the flame retardant composition of the present invention will be specifically described by taking a halogenated bisphenol type epoxy resin as an example of the halogenated epoxy resin flame retardant.

That is, a condensation reaction of a halogenated bisphenol with epichlorohydrin or a diglycidyl ether of a halogenated bisphenol obtained by the condensation reaction and a halogenated bisphenol are present in the presence of a catalyst.
A halogenated bisphenol type epoxy resin is obtained by heating and reaction at 100 to 230 ° C., then an inorganic flame retardant auxiliary agent and / or a coupling agent is added, and
By heat-melting and mixing at 0 ° C or by a condensation reaction of a halogenated bisphenol and epichlorohydrin, a diglycidyl ether of halogenated bisphenol is obtained, and the halogenated bisphenol and / or halogenated phenol is present in the glycidyl ether in the presence of a catalyst,
After reacting by heating at 100 to 230 ° C., an inorganic flame retardant auxiliary agent and / or a coupling agent is then added to 100 to 230
It can be produced by heating, melting, and mixing at 0 ° C.

Alternatively, the diglycidyl ether of a halogenated bisphenol and a halogenated bisphenol are reacted by heating at 100 to 230 ° C. in the presence of an inorganic flame retardant auxiliary and / or a coupling agent and a catalyst, or a halogenated bisphenol is added. Diglycidyl ether and halogenated bisphenol are heated and reacted at 100 to 230 ° C., and an inorganic flame retardant aid and / or a coupling agent is added during the reaction, or with diglycidyl ether of halogenated bisphenol. Halogenated bisphenol and / or halogenated phenol in the presence of an inorganic flame retardant aid and / or coupling agent and catalyst 10
The reaction is performed by heating at 0 to 230 ° C., or the diglycidyl ether of halogenated bisphenol and the halogenated bisphenol and / or halogenated phenol are added at 100 to 23.
It can be produced by reacting by heating at 0 ° C. and adding an inorganic flame retardant aid and / or a coupling agent during the reaction.

The flame retardant composition of the present invention can be produced by any of the methods (1) to (3) above, but the methods (1) and (2) are preferable because the generation of by-products and gelation products can be reduced.

Examples of the catalyst used here include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, tertiary amines such as dimethylbenzylamine, and 2-
Imidazoles such as ethyl-4-methylimidazole, quaternary ammonium salts such as tetramethylammonium chloride, phosphonium salts such as ethyltriphenylphosphonium iodide, and phosphines such as triphenylphosphine can be used.

The amount of the inorganic flame-retardant aid used in the present invention mixed with the halogenated epoxy resin-based flame retardant is remarkably excellent in impact resistance and flame-retardant effect, and the flame-retardant thermoplastic resin composition The range is preferably 1 to 50% by weight from the viewpoint of improving the fluidity. Above all, the range of 10 to 40% by weight is preferable from the viewpoint that the effect becomes more remarkable.

The amount of the coupling agent used in the present invention mixed with the halogenated epoxy resin flame retardant is in the range of 0.1 to 10% by weight from the viewpoint of excellent impact resistance improving effect. Above all, the range of 0.5 to 5% by weight is preferable because the impact resistance improving effect becomes more remarkable.

The thermoplastic resin which can be used in the present invention is not particularly limited, and examples thereof include polystyrene, rubber-modified polystyrene (HIPS resin), styrene resin such as acrylonitrile-butadiene-styrene copolymer (ABS resin), and polystyrene. Butylene terephthalate (PBT resin),
Polyester terephthalate (PET resin) and other polyester resins, ABS resin and polycarbonate resin alloys, ABS resin and polyester resin alloys such as A
Polymer alloy containing BS resin as one component, polyolefin resin such as polyethylene and polypropylene, polycarbonate resin, polyamide resin, polyphenylene oxide (PPO) resin, alloy of polycarbonate resin and polyester resin, polycarbonate resin and polyamide resin Alloys and the like, but the styrene resin, particularly HIPS, is excellent in compatibility with the flame retardant composition and has a more remarkable effect of improving impact resistance.
A polymer alloy containing a resin and an ABS resin, a polyester resin and an ABS resin as one component is preferable.

The flame retardant composition 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 composition of the present invention with respect to these thermoplastic resins is not particularly limited,
It is usually 1 to 50 parts by weight with respect to 100 parts by weight of the thermoplastic resin, and above all, 5 to 30 parts by weight is preferable in that the flame retardant effect is high and the deterioration of physical properties such as impact resistance is small.

As a method of blending the above-mentioned respective components, for example, there is a method of premixing with a mixer such as a Henschel mixer or a tumbler mixer, and then melt-kneading with an extruder, a kneader, a heat roll, a Banbury mixer or the like.

The resin composition containing the thermoplastic resin and the flame retardant of the present invention may further contain other chlorine-based flame retardants, bromine-based flame retardants and phosphorus-based flame retardants, if necessary. Depending on the UV absorber, light stabilizer, release agent, lubricant, colorant,
A plasticizer, a filler, a foaming agent, a heat stabilizer, a reinforcing material such as glass fiber, carbon fiber, and aramid fiber 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-2077. (2) Drop weight impact strength test (with notch) It was measured using a test piece having a thickness of 1/4 inch in accordance with JIS K721.

The weight used in the test was a steel spherical shape and had a HI
In the case of PS resin, the weight is 0.5 kg and the diameter is 50 mm (sphere 1 shape). In the case of ABS resin, the weight is 1 k.
g, diameter 50 mm (sphere 2 shape).

The impact strength is represented by the height (unit cm) when 50% of the number of test pieces is broken, and the vertical distance between the test pieces is 10 cm. (3) Izod impact strength test (with notch) It was measured using a test piece having a thickness of 1/4 inch in accordance with ASTM D-256.

Example 1 EPICLON 152, 545 g and TBP 455 g were placed in a 1 liter separable flask equipped with a thermometer and a stirrer, the inside was replaced with nitrogen gas, the contents were heated and melted, and hydroxylated at 100 ° C. 10% aqueous solution of sodium
After adding 0 g, the mixture was reacted at 160 to 170 ° C. for 7 hours. After the reaction, 250 g of antimony trioxide was added and further mixed at that temperature for 1 hour. Then, the mixture was poured into a stainless steel pan, cooled, and then pulverized to obtain a pale yellow flame retardant powder. This flame retardant has a softening point of 106 ° C and a bromine content of 4
It was 7% and the average degree of polymerization was 0.1. This is designated as flame retardant A.

Example 2 545 g of EPICLON 152 and 455 g of TBP were placed in a 1 liter separable flask equipped with a thermometer and a stirrer, the inside was replaced with nitrogen gas, the contents were heated and melted, and hydroxylated at 100 ° C. 10% aqueous solution of sodium
After adding 0 g, the mixture was reacted at 160 to 170 ° C. for 7 hours. After the reaction, 225 g of antimony trioxide and 25 g of 3-glycidoxypropyltrimethoxysilane (hereinafter abbreviated as silane coupling agent A) were added and further mixed at that temperature for 1 hour. Then, the mixture was poured into a stainless steel pan, cooled, and then pulverized to obtain a pale yellow flame retardant powder. This flame retardant had a softening point of 106 ° C., a bromine content of 47%, and an average degree of polymerization of 0.1. This is designated as flame retardant B.

Example 3 The procedure of Example 2 was repeated except that 25 g of isopropyl tris (dioctyl pyrophosphate) titanate (hereinafter referred to as titanium coupling agent A) was used instead of the silane coupling agent A. A yellow flame retardant powder was obtained. This flame retardant has a softening point of 106 ° C. and a bromine content of 47.
%, And the average degree of polymerization was 0.1. Flame retardant C
And

Example 4 Silane coupling agent A2 instead of antimony trioxide
A light yellow flame retardant powder was obtained in the same manner as in Example 1 except that 5 g was used. This flame retardant has a softening point of 9
It had a bromine content of 58% and an average degree of polymerization of 0.1 at 9 ° C. This is designated as flame retardant D.

Example 5 Titanium coupling agent A2 instead of antimony trioxide
A light yellow flame retardant powder was obtained in the same manner as in Example 1 except that 5 g was used. This flame retardant has a softening point of 9
It had a bromine content of 58% and an average degree of polymerization of 0.1 at 9 ° C. This is designated as flame retardant E.

EXAMPLE 6 808 g of EPICLON 152 and 192 g of TBA were placed in a 1 liter separable flask equipped with a thermometer and a stirrer, the inside was replaced with nitrogen gas, the contents were heated and melted, and hydroxylated at 100 ° C. 10% aqueous solution of sodium
After adding 7g, it was made to react at 160-170 degreeC for 7 hours. After the reaction, 250 g of antimony trioxide was added and further mixed at that temperature for 1 hour. Then, the mixture was poured into a stainless steel pan, cooled, and then pulverized to obtain a pale yellow flame retardant powder. This flame retardant has a softening point of 106 ° C and a bromine content of 4
The degree of polymerization was 0% and the average degree of polymerization was 1.1. This is designated as flame retardant F.

Example 7 808 g of Epiclon 152 and 192 g of TBA were placed in a 1 liter separable flask equipped with a thermometer and a stirrer, the inside was replaced with nitrogen gas, the contents were heated and melted, and hydroxylated at 100 ° C. 10% aqueous solution of sodium
After adding 7g, it was made to react at 160-170 degreeC for 7 hours. After the reaction, 225 g of antimony trioxide and 25 g of silane coupling agent A were added and further mixed at that temperature for 1 hour. Then, the mixture was poured into a stainless steel pan, cooled, and then pulverized to obtain a pale yellow flame retardant powder. This flame retardant had a softening point of 105 ° C., a bromine content of 40%, and an average degree of polymerization of 1.1. This is designated as flame retardant G.

Example 8 A pale yellow flame retardant powder was obtained in the same manner as in Example 7, except that 25 g of the titanium coupling agent was used instead of the silane coupling agent A. This flame retardant had a softening point of 105 ° C., a bromine content of 40%, and an average degree of polymerization of 1.1. This is designated as flame retardant H.

Example 9 Instead of antimony trioxide, silane coupling agent A2
A light yellow flame retardant powder was obtained in the same manner as in Example 6 except that 5 g was used. This flame retardant has a softening point of 9
It had a bromine content of 49% and an average degree of polymerization of 1.1 at 9 ° C. This is designated as flame retardant I.

Example 10 Titanium coupling agent A2 instead of antimony trioxide
A light yellow flame retardant powder was obtained in the same manner as in Example 6 except that 5 g was used. This flame retardant has a softening point of 9
It had a bromine content of 49% and an average degree of polymerization of 1.1 at 9 ° C. This is designated as flame retardant J.

Example 11 EPICLON 152, 556 g, TBA 113 g and T
BP331g was put in a 1 liter separable flask equipped with a thermometer and a stirrer, the inside was replaced with nitrogen gas, the contents were heated and melted, and 1.0g of 10% aqueous solution of sodium hydroxide was added at 100 ° C. After 170 to 180 ℃
And reacted for 7 hours. After the reaction, antimony trioxide 225
g and 25 g of the silane coupling agent A were added, and further mixed at that temperature for 1 hour. Then, the mixture was poured into a stainless steel pan, cooled, and then pulverized to obtain a pale yellow flame retardant powder. This flame retardant has a softening point of 122 ° C. and a bromine content of 45.
%, And the average degree of polymerization was 0.9. This is flame retardant K
And

Example 12 725 g of EPICLON 152 and 275 g of TBA were placed in a 1 liter separable flask equipped with a thermometer and a stirrer, the inside was replaced with nitrogen gas, the contents were heated and melted, and hydroxylated at 100 ° C. 10% aqueous solution of sodium
After adding 7g, it was made to react at 160-170 degreeC for 7 hours. After the reaction, 225 g of antimony trioxide and 25 g of lower silane coupling agent A were added and further mixed at that temperature for 1 hour. Then, the mixture was poured into a stainless steel pan, cooled, and then pulverized to obtain a pale yellow flame retardant powder. This flame retardant had a softening point of 135 ° C., a bromine content of 40%, and an average degree of polymerization of 2.2. This is designated as flame retardant L.

Example 13 A light yellow flame retardant powder was obtained in the same manner as in Example 12 except that 25 g of the titanium coupling agent A was used instead of the silane coupling agent A. This flame retardant is
Softening point 135 ° C, bromine content 40%, average degree of polymerization 2.2
It was the one. This is designated as flame retardant M.

Example 14 808 g of EPICLON 152, 192 g of TBA, 232 g of antimony trioxide and silane coupling agent A32
g and put in a 1 liter separable flask equipped with a thermometer and a stirrer, the inside was replaced with nitrogen gas, the contents were heated and melted, and 1.0 g of 10% aqueous solution of sodium hydroxide was added at 100 ° C. After that, the mixture was reacted at 160 to 170 ° C. for 7 hours. After the reaction, the mixture was poured into a stainless pan, cooled and pulverized to obtain a pale yellow flame retardant powder. This flame retardant had a softening point of 105 ° C., a bromine content of 40%, and an average degree of polymerization of 1.1. This is designated as flame retardant N.

Example 15 The same procedure as in Example 7 was conducted except that 25 g of 3-aminopropyltriethoxysilanesilane (hereinafter abbreviated as silane coupling agent B) was used instead of silane coupling agent A. A yellow flame retardant powder was obtained. This flame retardant had a softening point of 106 ° C., a bromine content of 40%, and an average degree of polymerization of 1.1. This is designated as flame retardant O.

Example 16 The procedure of Example 7 was repeated except that 25 g of acetomethoxyaluminum diisopropylate (hereinafter abbreviated as aluminum coupling agent A) was used in place of the silane coupling agent A, and a pale yellow color was obtained. A flame retardant powder was obtained.
This flame retardant had a softening point of 105 ° C., a bromine content of 40%, and an average degree of polymerization of 1.1. This is designated as flame retardant P.

Example 17 890 g of TBA and 228 g of epichlorohydrin were placed in a 3 liter flask equipped with a thermometer and a stirrer, the inside was replaced with nitrogen gas, and then 267 g of a 48% aqueous solution of sodium hydroxide was added. Then, it was made to react at 80 degreeC for 7 hours. After the reaction, 1000 g of methyl isobutyl ketone and 2 parts of water
Add 50 g and dissolve the reaction. After the dissolution, the mixture is allowed to stand and the organic layer and the saline layer are separated. Then, the alkali contained in the organic layer is completely neutralized with phosphoric acid and separated. The organic layer is distilled under reduced pressure at 170 ° C. to completely remove methyl isobutyl ketone. 225 g of antimony trioxide and 25 g of silane coupling agent A were added and further mixed at that temperature for 1 hour. The contents were poured into a stainless steel pan, cooled, and then pulverized to obtain 1250 g of a pale yellow flame retardant powder. This flame retardant had a softening point of 106 ° C., a bromine content of 40%, and an average degree of polymerization of 1.1. This is designated as flame retardant Q.

Example 18 604 g of EPICLON 152 and 396 g of TBA were placed in a 1 liter separable flask equipped with a thermometer and a stirrer, the inside was replaced with nitrogen gas, the contents were heated and melted, and hydroxylated at 100 ° C. 10% aqueous solution of sodium
After adding 5 g, the mixture was reacted at 195 to 205 ° C. for 8 hours. After the reaction, 417 g of antimony trioxide was added, and further mixed at that temperature for 1 hour. Then, the mixture was poured into a stainless steel pan, cooled, and then pulverized to obtain a pale yellow flame retardant powder. This flame retardant has a softening point of 191 ° C and a bromine content of 3
It was 7% and the average degree of polymerization was 15. This is flame retardant R
And Example 19 EPICLON 152 (604 g) and TBA (396 g) were placed in a 1 liter separable flask equipped with a thermometer and a stirrer, and the inside was replaced with nitrogen gas. Then, the contents were heated and melted, and sodium hydroxide (10 g) was added at 100 ° C. % Aqueous solution 1.
After adding 5 g, the mixture was reacted at 195 to 205 ° C. for 8 hours. After the reaction, 375 g of antimony trioxide and 42 g of silane coupling agent A were added and further mixed at that temperature for 1 hour. Then, the mixture was poured into a stainless steel pan, cooled, and then pulverized to obtain a pale yellow flame retardant powder. This flame retardant has a softening point of 190 ° C., a bromine content of 37%, and an average degree of polymerization of 1
It was 5. This is designated as the flame retardant S.

Example 20 A light yellow flame retardant powder was obtained in the same manner as in Example 19 except that 42 g of the titanium coupling agent A was used instead of the silane coupling agent A. This flame retardant is
The softening point was 190 ° C., the bromine content was 37%, and the average degree of polymerization was 15. This is designated as the flame retardant T.

Example 21 Silane coupling agent A4 instead of antimony trioxide
A light yellow flame retardant powder was obtained in the same manner as in Example 18 except that 2 g was used. This flame retardant had a softening point of 180 ° C., a bromine content of 50%, and an average degree of polymerization of 15. This is designated as flame retardant U.

Example 22 Titanium coupling agent A4 instead of antimony trioxide
A light yellow flame retardant powder was obtained in the same manner as in Example 18 except that 2 g was used. This flame retardant had a softening point of 180 ° C., a bromine content of 50%, and an average degree of polymerization of 15. This is designated as flame retardant V.

Reference Example 1 Tetrabromobisphenol A diglycidyl ether [EPICLON 15 manufactured by Dainippon Ink and Chemicals, Inc.
2, epoxy equivalent 360g / eq, bromine content 48%]
545 g and 2,4,6-tribromophenol (hereinafter T
455 g) is placed in a 1-liter separable flask equipped with a thermometer and a stirrer, the inside is replaced with nitrogen gas, the contents are heated and melted, and a 10% aqueous solution of sodium hydroxide at 100 ° C. 1 After adding 0.0 g, 160-1
The reaction was carried out at 70 ° C for 7 hours. After the reaction, the mixture was poured into a stainless pan, cooled and pulverized to obtain a pale yellow flame retardant powder. This flame retardant has a softening point of 100 ° C and a bromine content of 5
It was 9% and the average degree of polymerization was 0.1. This is designated as flame retardant a.

Reference Example 2 EPICLON 152, 556 g, tetrabromobisphenol A (hereinafter abbreviated as TBA) 113 g, and TBP32
5 g was put into a 1 liter separable flask equipped with a thermometer and a stirrer, the inside was replaced with nitrogen gas, the contents were heated and melted, and 1.0 g of a 10% aqueous solution of sodium hydroxide was added at 100 ° C. Then, the mixture was reacted at 170 to 180 ° C. for 7 hours. After the reaction, the mixture was poured into a stainless steel pan, cooled, and then pulverized to obtain a pale yellow flame retardant powder. This flame retardant had a softening point of 115 ° C, a bromine content of 56%, and an average degree of polymerization of 0.9. there were. This is designated as flame retardant b. Reference Example 3 808 g of EPICLON 152 and 192 g of TBA were placed in a 1 liter separable flask equipped with a thermometer and a stirrer, the inside was replaced with nitrogen gas, the contents were heated and melted, and sodium hydroxide 10 % Aqueous solution O.
After adding 7g, it was made to react at 160-170 degreeC for 7 hours. After the reaction, the mixture was poured into a stainless pan and cooled,
This flame retardant, which was crushed to obtain a pale yellow flame retardant powder, had a softening point of 100 ° C., a bromine content of 50%, and an average degree of polymerization of 1.1. This is designated as flame retardant c.

Reference Example 4 725 g of EPICLON 152 and 275 g of TBA were placed in a 1 liter separable flask equipped with a thermometer and a stirrer, the inside was replaced with nitrogen gas, the contents were heated and melted, and hydroxylated at 100 ° C. 10% aqueous solution of sodium
After adding 7g, it was made to react at 160-170 degreeC for 7 hours. After the reaction, the mixture was poured into a stainless pan and cooled,
This flame retardant, which was crushed to obtain a pale yellow flame retardant powder, had a softening point of 128 ° C., a bromine content of 50%, and an average degree of polymerization of 2.2. This is designated as flame retardant d.

Reference Example 5 604 g of EPICLON 152 and 396 g of TBA were placed in a 1 liter separable flask equipped with a thermometer and a stirrer, the inside was replaced with nitrogen gas, the contents were heated and melted, and hydroxylated at 100 ° C. 10% aqueous solution of sodium
After adding 5g, it was made to react at 190-210 degreeC for 8 hours. After the reaction, the mixture was poured into a stainless pan and cooled,
This flame retardant, which was crushed to obtain a pale yellow flame retardant powder, had a softening point of 182 ° C., a bromine content of 52%, and an average degree of polymerization of 15. This is designated as flame retardant e.

Examples 23 to 32 and Comparative Examples 1 to 6 Each component was blended in the composition shown in Table 1, premixed with a tumbler mixer, and pelletized with a 30 mmφ twin-screw extruder. Next, test pieces for various tests were prepared using a 5 ounce extruder, and a combustion test and a falling weight impact test were performed.

The results are shown in Table 1. The cylinder set temperature of the extruder and the injection molding machine was 220 to 230 ° C.

Examples 33 to 49 and Comparative Examples 7 to 18 The components were blended in the compositions shown in Table 2, premixed with a tumbler mixer, and pelletized with a 30 mmφ twin-screw extruder. Next, test pieces for various tests were prepared using a 5 ounce extruder, and a combustion test and a falling weight impact test were performed.

The results are shown in Table 2. The cylinder set temperature of the extruder and the injection molding machine was 230 to 240 ° C.

Examples 50 to 54 and Comparative Examples 19 to 22 The respective components were blended in the compositions shown in Table 2, premixed with a tumbler mixer, and pelletized with a 30 mmφ twin-screw extruder. Then, test pieces for various tests were prepared using a 5 ounce extruder, and a combustion test and Izod impact strength were measured.

The results are shown in Table 3. The cylinder set temperature of the extruder and the injection molding machine was 260 to 270 ° C. The test pieces were used for measuring Izod impact strength, and the results are shown in Table 3.

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

[Table 3]

[0067]

[Table 4]

[0068]

[Table 5]

[0069]

[Table 6]

[0070]

[Table 7] (In Tables 1 to 3, HIPS resin is a rubber modified polystyrene "GH-7000" manufactured by Dainippon Ink and Chemicals,
ABS resin is an acrylonitrile-butadiene-styrene copolymer "Cevian V" manufactured by Daicel Chemical Company, PBT resin is polybutylene terephthalate "Barox" manufactured by Nippon D-Plastics, and antimony trioxide is "ATOX-" manufactured by Nippon Mining Co., Ltd. F ". )

[0071]

INDUSTRIAL APPLICABILITY According to the present invention, a flame retardant composition which imparts remarkably excellent impact resistance to a thermoplastic resin and a flame retardant thermoplastic resin composition which is remarkably excellent in impact resistance, particularly falling weight impact strength. Can provide things.

Further, the molded product of the flame-retardant thermoplastic resin composition of the present invention is remarkably excellent in impact resistance and is therefore useful as a material for electric appliances, electronic parts, OA equipment and the like.

Claims (12)

[Claims] 1. A halogenated epoxy resin flame retardant (A).
A flame-retardant composition, characterized by being obtained by melt-mixing an inorganic flame-retardant auxiliary agent (B) and / or a coupling agent (C). 2. A halogenated epoxy resin flame retardant (A).
The flame retardant composition according to claim 1, which is obtained by melting and mixing the inorganic flame retardant auxiliary agent (B) and the coupling agent (C). 3. The flame retardant composition according to claim 1 or 2, wherein the inorganic flame retardant aid (B) is antimony oxide. 4. The flame retardant composition according to claim 1, 2 or 3, wherein the coupling agent (C) is a silane coupling agent. 5. A halogenated epoxy resin flame retardant (A).
And a thermoplastic resin (2), and a flame retardant composition (1) obtained by melting and mixing an inorganic flame retardant aid (B) and / or a coupling agent (C). Flame-retardant thermoplastic resin composition. 6. A flame-retardant composition (1) obtained by melting and mixing a halogenated epoxy resin-based flame retardant (A) with an inorganic flame-retardant auxiliary (B) and a coupling agent (C). The flame-retardant thermoplastic resin composition according to claim 5. 7. The flame-retardant thermoplastic resin composition according to claim 5, wherein the inorganic flame-retardant aid (B) is antimony oxide. 8. The flame-retardant thermoplastic resin composition according to claim 5, 6 or 7, wherein the coupling agent (C) is a silane coupling agent. 9. The flame-retardant thermoplastic resin composition according to claim 5, 6, 7 or 8, wherein the thermoplastic resin (2) is a styrene resin. 10. The flame-retardant thermoplastic resin composition according to claim 9, wherein the thermoplastic resin (2) is an acrylonitrile-butadiene-styrene copolymer. 11. The flame-retardant thermoplastic resin composition according to claim 9, wherein the thermoplastic resin (2) is a rubber-modified polystyrene. 12. The flame-retardant thermoplastic resin composition according to claim 5, 6, 7 or 8, wherein the thermoplastic resin (2) is a polyester resin.