JPH09235407A - Flame-retardant thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant thermoplastic resin compsn. excellent in flame retardancy with only a small amt. of a flame retarder by incorporating an ammonium polyphosphate compd. and a new amine phosphate thereinto. SOLUTION: This compsn. comprises a thermoplastic resin compounded with 1 to 30wt.%, based on the compsn., of an ammonium polyphosphate compd. and 1 to 30wt.%, based on the compsn., of an amine phosphate of the formula I n being 1 to 100; X being [R1 R2 N(CH2 )m NR3 R4 ] (R1 , R2 , R3 , and R4 being H or a C1 to C5 alkyl; and m being 1 to 10), piperazine or diamine containing a piperazine ring; and Y being NH3 or a triazine derivative of the formula II [Z1 and Z2 being -NR5 R6 (R5 and R6 being H, a 1-6C alkyl or methylol), hydroxyl, mercapto, 1-10C alkyl, 1-10C alkoxyl, phenyl or vinyl}.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant thermoplastic resin composition having excellent flame retardancy. More specifically, it relates to a flame-retardant thermoplastic resin composition having excellent flame retardancy, which is composed of a compound containing ammonium polyphosphate as a main component, a novel amine phosphate salt and a specific amount of a thermoplastic resin.

[0002] Thermoplastic resins have hitherto been utilized in fields such as industrial and household electric appliances by taking advantage of their sanitary properties, processability, chemical resistance, weather resistance, electrical characteristics and mechanical strength. As a result, it is widely used in various fields such as buildings, upholstery and automobile parts, and the applications in which thermoplastic resins are used are also expanding. With the expansion of such uses, the flame retardancy of thermoplastic resins has begun to be required, and the required performance has been stricter year by year. Particularly recently, a flame-retardant resin composition prepared by mixing a halogen-containing compound, which is the mainstream of conventional flame-retarding technology, alone or in combination with an antimony compound such as antimony oxide as a flame retardant, and blending it with a thermoplastic resin is However, generation of halogen-based gas at the time of combustion or molding is regarded as a problem.
Therefore, there is a demand for a flame-retardant resin composition that does not generate these halogen-based gases during combustion or molding.

In order to meet these demands, recently, a method has been proposed in which a specific metal hydrate capable of decomposing and dehydrating by an endothermic reaction at the combustion temperature of the resin to suppress the combustion of the resin is blended as an inorganic flame retardant. Has been done. However, in this method, the metal hydrate used has a very weak flame retardancy-imparting effect, so that it is necessary to add a large amount thereof, and as a result, the flame-retardant resin composition obtained has a poor moldability. However, there is a problem that various properties such as a decrease in mechanical strength of a molded product obtained from the composition are also deteriorated.

In order to meet the above requirements, a method using a specific phosphorus compound has been proposed. For example, JP-A-59-4
Japanese Patent No. 7285 proposes a fire prevention material in which ethylenediamine phosphate is combined with a salt of a melamine and / or cyanuric acid derivative, such as melamine phosphate. In addition, Japanese Patent Publication No. 5-508187 discloses a flame-retardant thermoplastic resin composition containing a phosphate such as alkyl diamine phosphate as a flame retardant. However, since ethylenediamine phosphate and alkyldiamine phosphate described in the publication have high water solubility, a fire prevention material or a flame-retardant thermoplastic resin composition containing such ethylenediaminephosphate or alkyldiamine phosphate is water-resistant. Has a problem that it cannot be used in applications where it comes into contact with moisture.

Further, Japanese Patent Application Laid-Open No. 63-277651 discloses a novel phosphite and a technique of applying it as a fire retardant, and Japanese Patent Publication No. 6-8308 discloses a wide range of resins and celluloses. A method for producing a condensed aminotriazine phosphate compound useful as a flame retardant for imparting flame retardancy to a base material is disclosed. However, since the novel phosphite and condensed aminotriazine phosphate compound obtained by the method disclosed in the publication do not contain a component having a foaming action in the compound components, a foaming action such as a polyhydric alcohol is obtained. There is a problem that a high degree of flame retardancy cannot be obtained unless it is used in combination with a certain component.

On the other hand, as a method of incorporating a foaming component into a compound, Japanese Examined Patent Publication No. 4-22916 and Japanese Examined Patent Publication No. 4-2.
Japanese Patent No. 1679 discloses that a novel amine salt of phosphoric acid or an amine salt of phosphoric acid is blended as a flame retardant additive for certain polymer compositions. However, in order to obtain the amine salt of phosphoric acid disclosed in the publication, it is necessary to use highly toxic phosphorus oxychloride as a starting material, and it cannot be produced without complicated steps, and it is industrially large-scaled. It has a problem that it is not advantageous for production.

[0007] Recently, in JP-A-6-87974 and JP-A-6-340770, a self-extinguishing property in which a salt of a specific triazine derivative and an oxygenated acid of phosphorus is blended with a thermoplastic resin as a flame retardant. Polymer compositions are disclosed. However, the compounds described in these publications also have a problem that they need to undergo complicated steps, and moreover, the addition amount must be increased in order to impart sufficient flame retardancy.

[0008]

DISCLOSURE OF THE INVENTION The present inventors have earnestly studied to obtain a flame-retardant thermoplastic resin composition which exhibits high flame retardancy even when the amount of the flame retardant is small. As a result, they have found that the above-mentioned problems can be solved by blending a thermoplastic resin with an ammonium polyphosphate compound and a novel amine phosphate salt, and the present invention has been completed based on this finding. As is clear from the above description, an object of the present invention is to provide a thermoplastic resin composition having excellent flame retardancy with a small amount of flame retardant added.

[0009]

The present invention provides the following (1) to
It has the configuration of (5). (1) 1 to 30% by weight of an ammonium polyphosphate compound (A) with respect to the composition of the thermoplastic resin, and (B) 1 to 3% of the amine phosphate represented by the following chemical formula 3 with respect to the composition.
A flame-retardant thermoplastic resin composition containing 30% by weight.

Embedded image (In the formula, n is an integer of 1 to 100, and X is [R ₁ R ₂ N
(CH ₂ ) _m NR ₃ R ₄ ], piperazine or a diamine containing a piperazine ring, wherein R ₁ , R ₂ , R ₃ and R ₄ are each H or a linear or branched alkyl group having 1 to 5 carbon atoms. And R ₁ , R ₂ , R ₃ and R ₄ may be the same or different. m is an integer of 1 to 10, and Y in the chemical formula ₃ is an NH ₃ group or a triazine derivative represented by the following chemical formula 4).

Embedded image (In the formula, Z ₁ and Z ₂ may be the same or different,
-NR ₅ R ₆ group (wherein R ₅ and R ₆ are the same or different H
Or a linear or branched alkyl group having 1 to 6 carbon atoms, or a methylol group], a hydroxyl group, a mercapto group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear chain having 1 to 10 carbon atoms, or Is a group selected from the group consisting of branched alkoxyl groups, phenyl groups, and vinyl groups).

(2) The ammonium polyphosphate compound is
General formula (NH ₄ ) _{r + 2} P _r O _{3r + 1} (where r is 20 to 10)
(Integer of 00), the flame-retardant thermoplastic resin composition according to (1), which is an ammonium polyphosphate or a compound containing ammonium polyphosphate as a main component. (3) A compound containing ammonium polyphosphate as a main component is formed from melamine monomer or melamine resin, modified melamine resin, guanamine resin, epoxy resin, phenol resin, urethane resin, urea resin and polycarbodiimide on the surface of the ammonium polyphosphate. The flame-retardant thermoplastic resin composition according to (2) above, which is a compound in which at least one selected from the group consisting of (4) A compound containing ammonium polyphosphate as a main component has a surface on which the ammonium polyphosphate is melamine monomer or melamine resin, modified melamine resin, guanamine resin, epoxy resin, phenol resin, urethane resin,
The flame-retardant thermoplastic resin composition according to (2) above, which is a compound which is coated or microencapsulated with at least one selected from the thermosetting resin group consisting of a urea resin and polycarbodiimide. (5) The thermoplastic resin is an olefin resin, styrene resin, polyamide resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polysulfone resin, thermoplastic polyurethane resin,
The flame-retardant thermoplastic resin composition according to any one of (1) to (4) above, which is one or more selected from a polyphenylene ether resin and a thermoplastic elastomer.

The ammonium polyphosphate compound, which is one of the constituent components of the flame-retardant thermoplastic resin composition of the present invention, is a simple substance of ammonium polyphosphate or a compound containing ammonium polyphosphate as a main component. The ammonium polyphosphate is a compound that can be represented by the general formula (NH ₄ ) _{r +2} P _r O _{3r + 1} (where r is an integer of 20 to 1000), and when r is sufficiently large, Formula (NH ₄ P
O ₃ ) _r (where r is the same as above) is a compound that can be approximated. As the ammonium polyphosphate, a commercially available product can be used, and as the commercially available product, exolit (Exo
lit) -422 (trade name, manufactured by Hoechst), Exorit
(Exolit) -700 (trade name, manufactured by Hoechst), Phoschek (Phos-chek) -P / 30 (trade name, manufactured by Monsanto), Phos-chek (Phos-chek) -P / 40 (trade name,
Monsanto), Sumisafe-P (trade name, manufactured by Sumitomo Chemical Co., Ltd.), TERRAJU-S10 (trademark,
Chisso Corporation), TERRAJU-S20
(Trademark, manufactured by Chisso Corporation).

As the compound containing ammonium polyphosphate as a main component, a compound obtained by coating or microencapsulating the ammonium polyphosphate with a thermosetting resin, a melamine monomer or another nitrogen-containing organic compound, etc. Ammonium acid A surface-coated product, a product treated with a surfactant or a silicon compound, and a product in which melamine or the like was added to make it insoluble in the process of producing ammonium polyphosphate, which was microencapsulated with a thermosetting resin. As a method for obtaining ammonium polyphosphate, for example,
A resin such as an epoxy resin, a urethane resin, an acrylic resin, a phenol resin, an alkyd resin, a urea resin, or a melamine resin is used alone or in combination as a resin to be coated, and a monomer of a desired coating resin component is formed on the surface of the ammonium polyphosphate.
Alternatively, an interfacial polymerization method or an in-situ polymerization method in which an oligomer is supported or attached and the monomer or oligomer is polycondensed (condensed), or an uncured but pre-completed polymer state is used. In-liquid curing method of coating ammonium polyphosphate surface with a coating resin and then curing the resin in a solvent, phase separation method utilizing a concentration gradient of the polymer solution by dissolving the coating polymer in a solvent, encapsulation A spray drying method in which the stock solution is sprayed and brought into contact with hot air to evaporate and dry the volatile components, the polymer to be coated is dissolved by heating in a solvent, ammonium polyphosphate is dispersed in this, and the solvent is volatilized while stirring. Alternatively, a known method such as an in-liquid drying method in which a film-forming polymer is precipitated by emulsifying and dispersing in a non-solvent and rapidly cooling can be mentioned.

The compound containing ammonium polyphosphate as a main component is commercially available as Exolit-
462 (trade name, manufactured by Hoechst), Sumisafe-PM
(Product name, Sumitomo Chemical Co., Ltd.), TERRAJ
U) -C60 (trademark, manufactured by Chisso Corporation), Terrage (T
ERRAJU) -C70 (trademark, manufactured by Chisso Corporation), TERRAJU-C80 (trademark, manufactured by Chisso Corporation) and the like.

The (B) amine phosphate salt, which is one of the constituents of the flame-retardant thermoplastic resin composition of the present invention, is a novel compound and can be obtained, for example, by the following method. That is, a reaction vessel is charged with a predetermined amount of phosphoric acid or condensed phosphoric acid having a degree of condensation of about 2 to 100 without adding an inert solvent or a solvent. Then, [R ₁ R ₂ N
A diamine represented by (CH ₂ ) _m NR ₃ R ₄ ] (wherein R ₁ , R ₂ , R ₃ and R ₄ are each H or have 1 carbon atom).
~ 5 straight-chain or branched alkyl groups, R ₁ , R
₂ , R ₃ and R ₄ may be the same or different. Further, m is an integer of 1 to 10), a compound which is a diamine containing piperazine or a piperazine ring (hereinafter collectively referred to as diamines) is added directly or dissolved in water or diluted with a solvent and added. , -10 to 10
React at 0 ° C. The reaction is a neutralization reaction and proceeds rapidly. Next, the reaction product formed here is isolated, or without isolation, ammonia or the triazine derivative represented by the above Chemical formula 4 is added with or without dilution with a solvent such as water, and the mixture is heated and reacted. By doing so, the novel amine phosphate salt of the present invention can be obtained. The amounts of diamines, ammonia and triazine derivatives involved in the reaction vary depending on the phosphoric acid or the phosphoric acid concentration of the condensed phosphoric acid used. That is, the amount of diamines to be added is less than ½ of the number of hydroxyl groups contained in phosphoric acid or condensed phosphoric acid, preferably, an approximately equimolar amount to phosphoric acid or condensed phosphoric acid is added, React to give an intermediate product. Then, an amount of ammonia or a triazine derivative corresponding to the hydroxyl group remaining in the intermediate product is added and reacted.

Specific examples of the diamines include N,
N, N ', N'-tetramethyldiaminomethane, ethylenediamine, N, N'-dimethylethylenediamine,
N, N'-diethylethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-diethylethylenediamine,
Tetramethylenediamine, 1,2-propanediamine,
1,3-propanediamine, tetramethylenediamine,
Pentamethylenediamine, hexamethylenediamine,
1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, piperazine, trans-2,5-dimethylpiperazine, 1,4-bis (2-aminoethyl) piperazine ,
1,4-bis (3-aminopropyl) piperazine and the like can be mentioned, and all commercially available products can be used.

Specific examples of the triazine derivative include melamine, acetoguanamine, benzoguanamine, acrylguanamine, 2,4-diamino-6-nonyl-1,3,5-triazine and 2,4-diamino-. 6-
Hydroxy-1,3,5-triazine, 2-amino-
4,6-dihydroxy-1,3,5-triazine,
2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-ethoxy-1,3,5-
Triazine, 2,4-diamino-6-propoxy-1,
3,5-triazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-
6-mercapto-1,3,5-triazine, 2-amino-4,6-dimercapto-1,3,5-triazine and the like can be mentioned, and all of them can be commercially available products.

Suitable thermoplastic resins as the base material of the flame-retardant thermoplastic resin composition of the present invention are various ones exemplified below: ◇ Polyolefin resin For example, polyethylene resin, polypropylene resin, poly One resin selected from -1-butene resin, poly-4-methyl-1-pentene resin, poly-1-hexene resin, poly-1-octene resin and poly-1-decene resin, or two or more thereof. A mixture (composition) of ◇ vinyl polymer resin such as polystyrene, poly-α-
Methylstyrene, polymethyl (meth) acrylate resin (PMMA), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer (AS resin), condensation polymerization type resin, for example, nylon (NY), heat Plastic polyester (PET, PBT, etc.), polycarbonate (PC), thermoplastic polyurethane (PU), polysulfone (PS), polyphenylene ether (PPE), ◇ thermoplastic elastomer (TPE or TPR) For example, olefin thermoplastic elastomer and styrene Examples of the thermoplastic elastomers include the following: -A polymer composition of the 1-olefin thermoplastic crystalline resin (PO) and an ethylene-propylene copolymer elastomer (EPM) or the polymer composition thereof. Coalescing composition Partially crosslinked products, - 1
-A polymer composition of an olefinic thermoplastic crystalline resin (PO) and an ethylene-propylene-non-conjugated diolefin copolymer elastomer (EPDM) or a partially crosslinked product of the polymer composition.

In the flame-retardant thermoplastic resin composition of the present invention, various additives usually added to the thermoplastic resin, such as an antioxidant, a heat resistance stabilizer, an anti-UV agent, an antistatic agent, and copper. Anti-harm agents, lubricants, neutralizing agents (higher fatty acid metal salts such as calcium stearate, zinc stearate, metal oxide / metal hydroxide complex salts such as hydrotalcite or manaceite), nucleating agents or pigments, etc. Can be used together.

The flame-retardant thermoplastic resin composition of the present invention can be produced, for example, by the following procedure. That is, a thermoplastic resin as a base, ammonium polyphosphate compound, a novel amine phosphate salt and other additives as required in predetermined amounts, respectively, in appropriate mixing devices such as a Henschel mixer (trade name) and a super mixer. Or put in a tumbler mixer, etc., then 1-10
Obtained by stirring and mixing for minutes. The obtained mixture is melt-kneaded at a temperature of 170 to 170 using a roll kneader or a screw extruder, and if necessary, an extruder with a vent.
The target flame-retardant resin composition can also be obtained by melting and kneading at 350 ° C., and then extruding the material into strands and cutting into pellets.

[0020]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, which by no means limit the scope of the present invention. The evaluation in Examples and Comparative Examples was performed by the following method.

(1) Flame retardance: UL94V UL Subject 94 (Underwriter Laboratories, Inc.) "vertical combustion test stipulated in" Combustion test of plastic material for parts of equipment ". Thickness of test piece 1.6 mm (1/16 inch) (2) Flame retardance: Oxygen index (O.I.) Based on Japanese Industrial Standard JIS K7201 (combustion test method for polymer materials by oxygen index method). (3) Bleed resistance test specimen (length 100 mm x width 100 mm x thickness 2 mm)
Was molded with an injection molding machine, and the surface electric resistance of the test piece was measured with a vibration capacitance type micro-current / electrometer (Advantest). Then, the test piece was allowed to stand in a constant temperature and constant humidity tank adjusted to a temperature of 80 ° C. and a humidity of 80%, taken out after 30 days, and the taken out test piece was placed in a constant temperature dryer controlled to a temperature of 80 ° C. for 2 days.
After being dried for an hour and allowed to stand at room temperature in a desiccator, the surface electric resistance of the test piece was measured. A test piece whose surface electric resistance value significantly decreased after 30 days was regarded as poor bleeding resistance under high temperature and high humidity conditions.

The novel amine phosphate salt used in each Example of the present invention was obtained by the following method.

Production Example 1 [Melamine salt of ethylenediamine phosphate (B
Preparation of 1)] In a reactor having a capacity of 1 liter equipped with a stirrer, a thermometer, a reflux condenser, and an inlet, 85% by weight of phosphoric acid 11 was added.
Add 5.3 parts by weight and 120 parts by weight of water at a temperature of 20-
60.2 parts by weight of ethylenediamine was added dropwise over 20 minutes while maintaining the temperature at 30 ° C., and then the mixture was heated with stirring at 60 ° C. for 1 hour. Then 600 parts by weight of water was placed in the reactor and 126.1 parts by weight (1 mol) of melamine was added with stirring,
The temperature was further raised to 80 ° C., and the temperature was maintained for 2 hours. After the completion of the reaction, the mixture was cooled, the product was filtered, washed, and dried in an oven at 105 ° C to obtain 241.6 parts by weight of a melamine salt (B1) of ethylenediamine phosphate.

Preparation Example 2 [Preparation of melamine salt of ethylenediamine pyrophosphate (B2)] 89 parts by weight of pyrophosphoric acid and 30 parts by weight of water were placed in a reactor having a capacity of 1 liter equipped with a stirrer, a thermometer, a reflux condenser and an inlet. 30.1 parts by weight of ethylenediamine was added dropwise over 10 minutes while maintaining the temperature at 20 to 30 ° C., and the mixture was further stirred at the same temperature for 1 hour. Then 6
00 parts by weight of water was placed in a reactor, 126.1 parts by weight (1 mol) of melamine was added with stirring, the temperature was further raised to 80 ° C., and the temperature was maintained for 2 hours. After the reaction, cool down
The product was filtered, washed, and dried in an oven at 105 ° C. to obtain a melamine salt of ethylenediamine pyrophosphate (B
2) 200 parts by weight was obtained.

Production Example 3 [Melamine salt of piperazine pyrophosphate (B3)]
Preparation] In a reactor having a capacity of 2 liters equipped with a stirrer, a thermometer, a reflux condenser, and an inlet, a solution prepared by dissolving 43.05 parts by weight of piperazine in 100 parts by weight of water was added at a temperature of 20 to 30 ° C.
A solution prepared by diluting 89 parts by weight of pyrophosphoric acid with 50 parts by weight of water was added dropwise while maintaining the above temperature, and the mixture was further stirred at the same temperature for 1 hour. Next, 650 parts by weight of water was put into the reactor, and 126.1 parts by weight of melamine was added with stirring.
The temperature was raised to 0 ° C. and the temperature was maintained for 2 hours. After the completion of the reaction, the mixture was cooled, the product was filtered, washed with water, and dried in an oven at 105 ° C. to obtain a piperazine pyrophosphate melamine salt (B
3) Obtained 250 parts by weight.

Production Example 4 [Melamine salt of piperazine polyphosphate (B4)]
Preparation] In a reactor having a capacity of 2 liters equipped with a stirrer, a thermometer, a reflux condenser, and an inlet, a solution prepared by dissolving 21.05 parts by weight of piperazine in 100 parts by weight of water was added at a temperature of 20 to 30 ° C.
A solution prepared by diluting 84.5 parts by weight of polyphosphoric acid (H ₆ P ₄ O ₁₃ ) with 50 parts by weight of water was added dropwise while maintaining the above temperature, and the mixture was further stirred at room temperature for 1 hour. Next, 650 parts by weight of water was put into the reactor, 126.1 parts by weight (1 mol) of melamine was added with stirring, and the temperature was further raised to 80 ° C.
Hold for hours. After the completion of the reaction, the mixture was cooled, the product was filtered, washed with water, and dried in an oven at 105 ° C to obtain 218.2 parts by weight of a melamine salt of piperazine polyphosphate (B4).

Example 1 Ammonium polyphosphate (Exolit-46
2) 8% by weight of (A1) and 1% of the melamine salt of ethylenediamine phosphate (B1) obtained in Production Example 1 above.
7% by weight and crystalline propylene as thermoplastic resin
Ethylene block copolymer [Ethylene component content 8.5
Weight%, MFR (temperature 230 ° C, load 2.16 Kgf)
20 g / 10 min. ] (C1) 73.7% by weight, hydrotalcite (D1) 0.8% by weight as various additives, 2,6-di-t-butyl-p-cresol (D2)
0.2 wt%, dimyristyl-β, β'-thiodipropionate (D3) 0.2 wt%, and calcium stearate (D4) 0.1 wt% were charged into a Henschel mixer (trade name) and stirred for 3 minutes. Mixed. The obtained mixture is melt-kneaded (temperature: 200 mm) using an extruder (caliber: 30 mm).
C.) and extruded to obtain pellets of the flame-retardant resin composition. After drying the obtained pellets at a temperature of 100 ° C. for 3 hours, the pellets were injected into an injection molding machine (cylinder temperature 220 ° C.).
Each of the predetermined test pieces was prepared by using (set to 0 ° C.) and evaluated for flame retardancy and bleed resistance. The results are shown in Table 1.

Examples 2 to 5 Melt kneading and extrusion were carried out in accordance with Example 1 except that the composition was changed as shown in Table 1 to prepare pellets. Predetermined test pieces were prepared in accordance with Example 1 using the obtained pellets, and flame retardancy and blade resistance were evaluated using the test pieces. The results are shown in Table 1.

Example 6 Ammonium polyphosphate (TERRAJU-M3)
0) 10% by weight of (A3), the melamine salt of ethylenediamine pyrophosphate (B) obtained in Production Example 2 above.
15% by weight of 2) and vinyltrimethoxysilane (D5) which is a silane coupling agent as other additives.
0.8% by weight was charged into a Henschel mixer (trade name) and stirred and mixed for 3 minutes. Next, high density polyethylene [MI (temperature 190 ° C, load 2.16Kg
f) 6.5 g / 10 min. Product name: Chisso Polyech M680 (manufactured by Chisso Corporation)] (C2) 73% by weight,
0.7% by weight of hydrotalcite (D1), 2,6-di-t-butyl-p-cresol (D) as various additives
2) 0.2 wt%, dimyristyl-β, β′-thiodipropionate (D3) 0.2 wt%, and calcium stearate (D4) 0.1 wt% were additionally charged, and the mixture was further stirred and mixed for 3 minutes. The obtained mixture is an extruder (caliber 30 m
m) was melt-kneaded (temperature: 200 ° C.) and extruded to obtain pellets of the flame-retardant resin composition. 1 of the obtained pellets
After drying at a temperature of 00 ° C. for 3 hours, the pellets were used to prepare predetermined test pieces using an injection molding machine (cylinder temperature was set to 220 ° C.), and flame retardancy and bleed resistance were evaluated. . The results are shown in Table 1.

Example 7 Ammonium polyphosphate (TERRAJU-C6)
0) 15% by weight of (A2) and 1% of the melamine salt (B3) of piperazine pyrophosphate obtained in Preparation Example 3 above.
5 wt%, polystyrene resin [MI as thermoplastic resin
(Temperature 190 ° C, load 2.16Kgf) 14.0g / 1
0 min. Product name: Styron 470 (manufactured by Asahi Kasei Corporation)] (C3) 68.8% by weight, and hydrotalcite (D1) 0.7% by weight as various additives are charged into a Henschel mixer (product name) and stirred for 3 minutes Mixed. The obtained mixture was melt-kneaded (temperature: 200 ° C.) using an extruder (diameter: 30 mm) and extruded to obtain pellets of a flame-retardant resin composition. The obtained pellets were dried at a temperature of 100 ° C. for 3 hours, and then the pellets were injected into an injection molding machine (cylinder temperature 2
Each predetermined test piece was prepared by using (set at 20 ° C.) and evaluated for flame retardancy and bleed resistance. Table 1 shows the results.
It was shown to.

Example 8 Ammonium polyphosphate (TERRAJU-C6)
0) 5% by weight of (A2) and 25% of the melamine salt (B4) of piperazine polyphosphate obtained in the above Production Example 4
% By weight, ABS resin [MI (temperature 1
90 ° C., load 2.16 Kgf) 15 g / 10 min. ;
Product name: Styrac 101 (Made by Asahi Kasei)] (C
4) 68.8% by weight and 0.7% by weight of hydrotalcite (D1) as various additives were charged into a Henschel mixer (trade name) and mixed with stirring for 3 minutes. The obtained mixture is melt-kneaded (temperature: 210 mm) using an extruder (caliber: 30 mm).
C.) and extruded to obtain pellets of the flame-retardant resin composition. After drying the obtained pellets at a temperature of 100 ° C. for 3 hours, the pellets were injected into an injection molding machine (cylinder temperature 220 ° C.).
Each of the predetermined test pieces was prepared by using (set to 0 ° C.) and evaluated for flame retardancy and bleed resistance. The results are shown in Table 1.

Example 9 Ammonium polyphosphate (TERRAJU-M3)
0) 7% by weight of (A3), the melamine salt of ethylenediamine pyrophosphate (B2) obtained in Production Example 2
7% by weight, 7% by weight of the melamine salt of piperazine polyphosphate (B4) obtained in Production Example 4 above, and a crystalline propylene-ethylene block copolymer [ethylene content 8.5% as a thermoplastic resin. %, MFR (temperature 230 ° C., load 2.16 Kgf) 20 g / 10 mi
n. 57.7% by weight of (C1), high density polyethylene [MI (temperature 190 ° C., load 2.16 Kgf) 6.5 g
/ 10 min. Product name: Chisso Polyech M680 (manufactured by Chisso Corporation)] (C2) 10% by weight, ethylene-
Propylene rubber [trade name: EP-02P (manufactured by Japan Synthetic Rubber Co., Ltd.)] (C5) 10% by weight, hydrotalcite (D1) 0.8% by weight as various additives, 2,6-di-t
-Butyl-p-cresol (D2) 0.2% by weight, dimyristyl-β, β'-thiodipropionate (D3)
0.2% by weight, calcium stearate (D4) 0.1
The weight% was charged into a Henschel mixer (trade name) and mixed by stirring for 3 minutes. The obtained mixture is an extruder (caliber 30 m
m) was melt-kneaded (temperature: 200 ° C.) and extruded to obtain pellets of the flame-retardant resin composition. 1 of the obtained pellets
After drying at a temperature of 00 ° C. for 3 hours, the pellets were used to prepare predetermined test pieces using an injection molding machine (cylinder temperature was set to 220 ° C.), and flame retardancy and bleed resistance were evaluated. . The results are shown in Table 1.

Comparative Example 1 Melamine salt of ethylenediamine phosphate (B1)
A thermoplastic resin composition was obtained according to Example 1 except that melamine was used instead of, and each test piece was prepared according to Example 1, and flame retardancy and bleed resistance were evaluated. . The results are shown in Table 1.

Comparative Example 2 Melamine salt of ethylenediamine phosphate (B1)
A thermoplastic resin composition was obtained in the same manner as in Example 1 except that ethylenediamine phosphate was used instead of
Each test piece was prepared in accordance with the above, and the flame retardancy and bleeding resistance were evaluated. The results are shown in Table 1.

Comparative Example 3 Ammonium polyphosphate (TERRAJU-M3)
A thermoplastic resin composition was obtained according to Example 6 except that diammonium dihydrogen phosphate was used instead of 0), and each test piece was prepared according to Example 1 to obtain flame retardance and The bleeding resistance was evaluated. The results are shown in Table 1.

[0036]

EFFECT OF THE INVENTION The flame-retardant thermoplastic resin composition of the present invention obtained by blending an ammonium polyphosphate compound and a novel amine phosphate salt with a thermoplastic resin exhibits excellent flame retardancy at a low addition amount. Moreover, since it is also excellent in bleeding resistance, the molded article using the composition can be more suitably used in the fields of electrical products, building materials, automobile parts and the like.

[0037]

[Table 1]

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location C08L 101/00 C08L 101/00

Claims (5)

[Claims] 1. A thermoplastic resin containing (A) ammonium polyphosphate
1 to 30% by weight of the compound, based on the composition, and
(B) An amine phosphate represented by the following chemical formula 1 is added to the composition.
Flame retardant heat characterized by being blended in an amount of 1 to 30% by weight
Plastic resin composition. [Chemical 1](In the formula, n is an integer of 1 to 100, and X is [R₁R_TwoN
(CH_Two)_mNR_ThreeR_Four], Piperazine or piperazine
A diamine containing a ring, R₁, R_Two, R_ThreeAnd R_FourHaso
H or a straight or branched chain having 1 to 5 carbon atoms, respectively.
A alkyl group;₁, R_Two, R_ThreeAnd R_FourAre the same group
May be different. m is an integer of 1 to 10
And in the formula 1, Y is NH_ThreeGroup or below
Is a triazine derivative represented by). Embedded image(In the formula, Z₁And Z_TwoMay be the same or different,
-NR_FiveR₆Group [where R _Five, R₆Are the same or different H
Alternatively, a straight-chain or branched alkyl having 1 to 6 carbon atoms
Group or methylol group], hydroxyl group, mercapto group, charcoal
Linear or branched alkyl group having a prime number of 1 to 10, carbon number
1-10 linear or branched alkoxyl groups, phenyl
A group selected from the group consisting of a vinyl group and a vinyl group.
). 2. An ammonium polyphosphate compound is ammonium polyphosphate or ammonium polyphosphate represented by the general formula (NH ₄ ) _{r + 2} P _r O _{3 r + 1} (where r is an integer of 20 to 1000). The flame-retardant thermoplastic resin composition according to claim 1, which is a compound having a main component. 3. A compound containing ammonium polyphosphate as a main component, wherein a melamine monomer or a melamine resin, a modified melamine resin, a guanamine resin, an epoxy resin, a phenol resin, a urethane resin, a urea resin and a polyamine are formed on the surface of the ammonium polyphosphate. The flame-retardant thermoplastic resin composition according to claim 2, wherein one or more thermosetting resins selected from the thermosetting resin group consisting of carbodiimide are present. 4. A compound containing ammonium polyphosphate as a main component, wherein the ammonium polyphosphate is a melamine monomer or melamine resin, modified melamine resin, guanamine resin, epoxy resin, phenol resin, urethane resin,
The flame-retardant thermoplastic resin composition according to claim 2, which is coated or microencapsulated with at least one selected from the thermosetting resin group consisting of a urea resin and polycarbodiimide. 5. The thermoplastic resin is selected from olefin resins, styrene resins, polyamide resins, polycarbonate resins, polyethylene terephthalate resins, polybutylene terephthalate resins, polysulfone resins, thermoplastic polyurethane resins and polyphenylene ether resins, and thermoplastic elastomers. It is 1 or more types, 1-4.
The flame-retardant thermoplastic resin composition according to any one of 1.