JPH07196845A - Flame-retardant thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a flame-retardant thermoplastic resin composition which can give a molding excellent in bleeding resistance and flame retardancy and therefore nonproblematic in irreversible bleeding of ammonium polyphosphate to the surface of a molding made of a composition comprising a thermoplastic resin and ammonium polyphosphate. CONSTITUTION:This composition comprises 10-40wt.% insoluble ammonium polyphosphate particles characterized in that the surface of each particle is cross-linked with the active hydrogen atom of the amino group of a melamine molecule present on the coating layer of an ammonium polyphosphate particle coated with melamine and a compound having a functional group reactive with active hydrogen, 1-20wt.% nitrogenous organic compound, and 89-40wt.% thermoplastic resin (the total amount of the above component being 100wt.%).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition containing insoluble ammonium polyphosphate and having excellent flame retardancy. More specifically, (A) insoluble ammonium polyphosphate in which a crosslinked structure is formed on the outermost periphery of melamine-coated ammonium polyphosphate, (B) nitrogen-containing organic compound, (C)
The present invention relates to a thermoplastic resin composition which is made of a thermoplastic resin and has excellent water resistance and flame retardancy.

[Prior art]

[0002] Conventionally, polyolefin resins have taken advantage of their processability, chemical resistance, weather resistance, electrical characteristics, mechanical strength, etc., to make use in the fields of industrial and household electric appliances, as well as buildings and indoors. It is widely used in various fields such as ornaments and automobile parts, and the applications in which thermoplastic resins are used are also expanding. With the expansion of such applications, the thermoplastic resin is beginning to be required to have flame retardancy, and the required performance is becoming severer year by year. Particularly recently, a flame-retardant resin composition in which a halogen compound, which is the mainstream of conventional flame-retarding technology, is mixed with a thermoplastic resin, or a flame-retardant resin composition in which a halogen-containing compound and antimony oxide are mixed with a thermoplastic resin is burned. It is regarded as a problem because halogen-based gas is generated during molding or molding. Therefore, there is a growing demand for flame-retardant resin compositions that do not generate these halogen-based gases during combustion and molding.

In order to meet these demands, recently, ammonium polyphosphate and non-flammable gas (water,
Carbon dioxide, ammonia, nitrogen, etc.) and one or more nitrogen-containing organic compounds that produce carbonaceous residues have been proposed as flame-retardant resin compositions. For example,
JP-A-59-147050, EP-047541
JP-A No. 8-146 proposes a flame-retardant composition comprising a polymer or oligomer of a 1,3,5-triazine derivative and ammonium polyphosphate.
No. 452, a> C = 0 group inserted in a cyclic structure,
A flame-retardant composition comprising a reaction product of a nitrogen compound having a C = S group or> NH group with an aldehyde and ammonium polyphosphate is disclosed in JP-A-55-129435. A flame-retardant composition composed of a reaction product and ammonium polyphosphate is proposed, and JP-A-54-53156 proposes a flame-retardant composition composed of a derivative of isocyanuric acid and ammonium polyphosphate. Further, as a combination other than the nitrogen-containing compound, JP-A 64-14277 proposes a flame-retardant composition comprising a high-viscosity silicone oil, a silicone resin, a polyhydric alcohol and ammonium phosphates.

However, the above-mentioned conventional flame-retardant composition has a high flame-retardant effect, but ammonium polyphosphate in the composition is very susceptible to hydrolysis due to its chemical structure.
Due to the hygroscopicity, water solubility, and hydrolyzability of ammonium polyphosphate, the ammonium polyphosphate is formed on the surface of a molded article obtained by molding using the resin composition under high temperature and high humidity conditions such as the rainy season. The phenomenon of bleeding violently occurs. Furthermore, since the nitrogen-containing organic compound described in EP-0475418 has hygroscopicity, ammonium polyphosphate is easily hydrolyzed, and the hydrolyzate easily bleeds on the surface of a molded article, resulting in flame retardancy. A molded product using the resin composition has a drawback that the electric resistance value on the surface of the molded product is significantly reduced and the molded product cannot be used as an electrical insulating material under high temperature and high humidity conditions.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have found that even if a flame-retardant thermoplastic resin composition containing ammonium polyphosphate is used, a molded article obtained by using the composition bleeds under high temperature and high humidity conditions. Intensive research was conducted in order to obtain a flame-retardant thermoplastic resin composition which gives a molded product with almost no phenomenon. As a result, melamine is added and / or attached by sublimation to the surface of ammonium polyphosphate particles by sublimation instead of conventional ammonium polyphosphate to obtain melamine-coated ammonium polyphosphate particles, and an amino group in the melamine molecule present in the particle surface coating layer. To reduce the flame retardancy of a molded article by using ammonium polyphosphate as an insoluble ammonium polyphosphate obtained by cross-linking the active hydrogen belonging to the group with a compound having a functional group capable of reacting with the active hydrogen. It has been found that a composition which solves the above-mentioned problems can be obtained without any generation of decomposition gas and the like during combustion or molding, and the present invention has been completed based on this finding. As is clear from the above description,
The object of the present invention is to solve the bleeding phenomenon of ammonium polyphosphate on the surface of the molded article that the molded article using the composition in which ammonium polyphosphate is mixed with the thermoplastic resin inevitably has excellent bleed resistance and flame retardancy. Another object of the present invention is to provide a thermoplastic resin composition capable of obtaining a molded product.

[0006]

The bleed-resistant and flame-retardant polyolefin resin composition of the present invention has the following constitution. 1) Flame-retardant thermoplastic resin composition comprising the following components (A), (B), and (C) in a total amount of 100% by weight: (A) present in a coating layer of melamine-coated ammonium polyphosphate particles Insoluble ammonium polyphosphate particles characterized in that the surface of the particle is crosslinked by active hydrogen belonging to the amino group in the melamine molecule and a compound having a functional group capable of reacting with the active hydrogen: 10 to 40% by weight % (B) Nitrogen-containing organic compound: 1 to 20% by weight (C) Thermoplastic resin: 89 to 40% by weight (2) A compound having a functional group capable of reacting with active hydrogen belonging to an amino group in a melamine molecule Isocyanate group,
The flame-retardant thermoplastic resin composition according to item 1, which is a compound having a glycidyl group, a carboxyl group, a methylol group or an aldehyde group. (3) The flame-retardant thermoplastic resin composition according to the above item 1, wherein the compound having a functional group capable of reacting with active hydrogen belonging to an amino group in a melamine molecule has one or two or more functional groups. (4) The flame-retardant heat according to item 1, wherein the melamine-coated ammonium polyphosphate is a melamine-coated ammonium polyphosphate obtained by coating powdery ammonium polyphosphate with 0.5 to 20% by weight of melamine. Plastic resin composition (5) The flame-retardant thermoplastic resin according to item 1, wherein the nitrogen-containing organic compound is a homopolymer and / or a copolymer containing a monomer having a structure represented by the following chemical formula 2 as a basic unit. Composition

[Chemical 2] (Wherein X and Z ¹ are both structures bonded to a triazine skeleton through a nitrogen atom, and X is an alkylamino group or a morpholino group represented by a group of —NHR ¹ or —NR ² R ³ , It is a piperidino group and R ¹ , R ² and R ³ are linear or branched alkyl groups having 1 to 6 carbon atoms (R ² and R ³ may be the same or different). Alternatively, X is a hydroxyalkylamino group represented by the group —NHR ⁴ —NR ⁵ R ⁶ and R ⁴ , R ⁵ and R ⁶ have 2 carbon atoms.
A linear or branched hydroxyalkyl group having 6 to 6 (R ⁵ and R ⁶ may be the same or different). Z ¹ is a divalent group of piperazine, or is of the formula —HN
(CH ₂₎ 2 divalent group represented by MNH- (the m is an integer from 2 to 6), or -NR ⁷ (CH ₂₎ a _l R ⁸ N-a group represented by R ^7, R One or both of ⁸ is a hydroxyethyl group. (6) The flame-retardant thermoplastic resin composition according to item 1, wherein the nitrogen-containing organic compound is a reaction product obtained by reacting cyanuric chloride and a diamine. (7) The flame-retardant thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is an aliphatic thermoplastic resin, an aromatic thermoplastic resin, an elastomer thereof, or a mixture of two or more thereof.

The insoluble ammonium polyphosphate which is the component (A) used in the present invention is the active hydrogen attributed to the amino group in the melamine molecule present in the melamine coating layer of the melamine-coated ammonium polyphosphate, isocyanate group, glycidyl group or It is ammonium polyphosphate in which a crosslinked structure is formed between melamine molecules on the same particle by reacting a compound having a functional unit capable of reacting with the active hydrogen such as an aldehyde group. A melamine-coated ammonium polyphosphate and a compound having a functional group capable of reacting with active hydrogen belonging to an amino group in a melamine molecule, for example, an aqueous formaldehyde solution are charged into a reactor equipped with a heating stirring or kneading mechanism. The temperature at which a crosslinked structure between active hydrogen is easily formed is 80 to 200 ° C., preferably 10
It is possible to obtain insoluble ammonium polyphosphate having a crosslinked structure formed in the coating layer of the melamine-coated ammonium polyphosphate particles by heating to 0 to 150 ° C. and reacting for 0.5 to 2 hours. . This crosslinking reaction may be either a non-solvent system or a solvent system, and the solvent system may be water, an organic solvent or a mixed solvent composed of two or more kinds of these solvents. The functional group contained in the crosslinking agent is 0.5 to 6 times equivalent, preferably 1 to 2 times equivalent to the amino group in the melamine molecule of the melamine-coated ammonium polyphosphate. If it is less than 0.5, the melamine is not sufficiently crosslinked and is easily hydrolyzed. On the other hand, when the amount is more than 6 times equivalent, unreacted substances remain, which is not preferable. Isocyanate group as the functional group that reacts with the active hydrogen attributed to the amino group in the melamine molecule,
It is a glycidyl group, a carboxyl group, a methylol group or an aldehyde group, and the number of the functional groups is monofunctional or polyfunctional. Examples of the compound having the functional group include hexamethylene diisocyanate, toluylene diisocyanate, various epoxy resins represented by bisphenol A and phenol novolac, oxalic acid, malonic acid,
Examples thereof include phthalic acid, trimethylolpropane, trimethylolethane, formaldehyde, glyoxal and malonic aldehyde.

Further, the melamine-coated ammonium polyphosphate is a product obtained by adding and / or adhering melamine to the surface of ammonium polyphosphate particles, and such melamine-coated ammonium polyphosphate can be obtained by the following method. That is, the temperature of the ammonium polyphosphate particles is charged into a heating kneader such as a heated kneader, the ammonium polyphosphate particles are not melted, and ammonia in the ammonium polyphosphate is easily desorbed. 300 ° C or less, preferably 200 to 300 ° C
Was heated for 0.5 to 5 hours to desorb a part of the ammonia (5 to 10% by weight based on the stoichiometric amount of ammonia) originally present in the ammonium polyphosphate in the stoichiometric amount. Ammonia deficient ammonium polyphosphate or ammonium polyphosphate in a known production process of ammonium polyphosphate in a state where the amount of bonded ammonia is less than the stoichiometric amount (hereinafter, these are referred to as ammonia deficient ammonium polyphosphate) Then, in the same device, the ammonia-deficient ammonium polyphosphate particles are heated at a temperature at which the ammonia-deficient ammonium polyphosphate particles do not melt and at a temperature of 250 to 300 ° C., which is a temperature at which melamine can sublime. Ammonia on the particle surface is desorbed to form an acid, and the hydroxyl group An addition and / or attaching Min. Addition means a state in which melamine is ionically bound to a proton of an oxygen-proton bond derived from ammonium polyphosphate, and the added melamine is stable even when heated and does not desorb again. Further, the adhesion means a state in which melamine is adsorbed on the surface of the ammonium polyphosphate particles, and the melamine adsorbed on the surface of the ammonium polyphosphate particles by continued heating repeats sublimation and adsorption and oxygen-proton-bonded protons and ions. Join together. The proportion of melamine added at this time is 0.5 to 20% by weight with respect to the ammonium polyphosphate, preferably 2 to 20% by weight.
The amount of melamine added is 10% by weight, and the whole amount of the added melamine is added and / or attached to the ammonium polyphosphate to obtain a melamine-coated ammonium polyphosphate.

Commercially available ammonium polyphosphate may be used as the raw material of the melamine-coated ammonium polyphosphate. Examples of commercially available products include Sumisafe-P (trademark, manufactured by Sumitomo Chemical Co., Ltd.) and Exolit-422 ( Trademark,
Hoxist), Exolite-700 (trademark, manufactured by Hoechst), Foscheck P / 40 (trademark, manufactured by Monsanto), and the like, and II type ammonium polyphosphate fine particles can also be used. The type II ammonium polyphosphate fine particles can be obtained, for example, by the following method. That is, equimolar amounts of diammonium phosphate and phosphorus pentoxide were mixed, heated and stirred at a temperature of 290 to 300 ° C., and then 0.5 times mol of urea was dissolved in diammonium phosphate to give a concentration of 77% by weight. Add while spraying urea solution,
Continuously under ammonia atmosphere for several hours, temperature 250-2
It is obtained by a method of baking at 70 ° C. The melamine used may be a commercially available melamine monomer.

The compounding ratio of the insoluble ammonium polyphosphate is usually 10 to 40% by weight, preferably 1 based on the composition.
It is 5 to 25% by weight. If the blending ratio is less than 7% by weight, sufficient flame retardancy cannot be obtained, and if the blending ratio exceeds 50% by weight, flame retardancy is hardly improved.

The component (B) used in the present invention, the nitrogen-containing organic compound, means a non-flammable gas (when present together with insoluble ammonium polyphosphate in a thermoplastic resin) due to thermal decomposition due to ignition or contact with a flame ( Water, carbon dioxide,
Ammonia, nitrogen, etc.) and organic compounds that generate only a carbonaceous residue, specifically, a homopolymer and / or a copolymer having the monomer structure represented by Chemical Formula 2 as a basic unit. , For example, 2-piperazinylene-4-morpholino-1,3,5-triazine,
2-piperazinylene-4-piperidino-1,3,5-triazine, 2-piperazinylene-4-N, N bis (hydroxyethyl) amino-1,3,5-triazine, 2-
Piperazinylene-4-N-hydroxyethylamino-
Homopolymers and / or copolymers containing 1,3,5-triazine as a monomer unit can be mentioned. Further, a reaction product obtained by reacting cyanuric acid chloride with diamines, preferably a reaction product obtained by reacting cyanuric acid chloride with diamines at a molar ratio of 2: 3, for example, cyanuric acid chloride with ethylenediamine A reaction product obtained by reacting at a ratio of 2: 3 and a reaction product obtained by reacting cyanuric acid chloride and 1,3-diaminopropane at a molar ratio of 2: 3 can also be used.

In addition to the above-mentioned nitrogen-containing organic compounds, known nitrogen-containing organic compounds, for example, inserted in a cyclic structure>
Reaction product of nitrogen compound containing C = 0 group,> C = S group or> NH group with aldehyde, reaction product of benzylguanamine with aldehyde or tris (2-hydroxyethyl) isocyanurate, tris (3 -Hydroxy-N-propyl) isocyanurate, tris (2,3
A nitrogen-containing organic compound which is a derivative of isocyanuric acid such as -epoxypropyl) isocyanurate can be blended. Further, instead of the nitrogen-containing compound, high-viscosity silicone oil and / or silicone resin and polyhydric alcohol can be blended. Instead of the polyhydric alcohol, magnesium stearate which is a 2A group metal salt of carboxylic acid may be used. The high-viscosity silicone oil is an essentially linear polydimethylsiloxane polymer having a viscosity of about 90,000 to 150,000 centipoise at 25 ° C., and the silicone resin is an average formula (R ⁹ ) ₃
It is an MQ silicone resin consisting of monofunctional M units of SiO _0.5 and tetrafunctional Q units of the average formula SiO ₂ , and the ratio of M units to Q units is 0.3 to 0.4. Furthermore, examples of the polyhydric alcohol include pentaerythritol, dipentaerythritol, and tripentaerythritol. The silicone oil, silicone resin, polyhydric alcohol and the like are not particularly limited, and commercially available products that are usually commercially available can be used as they are. The blending ratio of the component (B) is usually 1 to 20% by weight based on the composition. The blending ratio is 1
If it is less than 5% by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 25% by weight, further improvement in flame retardancy is hardly seen.

The above-mentioned 2-piperazinylene-4-morpholino-1,3,5 which is one of the nitrogen-containing organic compounds.
-To obtain a homopolymer having triazine as a monomer unit, equimolar amounts of 2,6-dihalo-4-morpholino-1,3,3
5-triazine (for example, 2,6-dichloro-4-morpholino-1,3,5-triazine or 2,6-dibromo-4-morpholino-1,3,5-triazine) and piperazine are combined with an organic or inorganic base ( For example, the reaction is carried out under heating in an inert solvent such as xylene in the presence of triethylamine, tributylamine, sodium hydroxide, potassium hydroxide, or sodium carbonate). After the completion of the reaction, the reaction compound is filtered to separate a solid matter, and the solid matter is washed with boiling water to remove a by-product salt, and then the solid matter is dried. The obtained 2-piperazinylene-4-morpholino-
A homopolymer containing 1,3,5-triazine as a monomer unit is insoluble in ordinary organic solvents, has no melting point, has a decomposition temperature of about 304 ° C., and has a true density of 1.3 g / cc.

Further, when a homopolymer having 2-piperazinylene-4-bis (hydroxyethyl) amino-1,3,5-triazine as a monomer unit is obtained, 2,6-dihalo-4-bis (hydroxyethyl) is also obtained. Amino-1,3,5
-The method based on the above can be applied using triazine as a raw material. Furthermore, 2-piperazinylene-4-morpholino-1,3,5-triazine and 2-piperazinylene-4-bis (hydroxyethyl) amino-1,3,5
-To obtain a copolymer containing triazine as a monomer unit, 2,6-dihalo-4-morpholino-1,3,5-triazine and 2,6-dihalo-4-bis (hydroxyethyl) amino-1,3,3 The method based on the above can be applied using a mixture of 5-triazine as a raw material. 2,6-dihalo-4-morpholino-1,3,5-triazine and 2,
6-dihalo-4-bis (hydroxyethyl) amino-1,
By arbitrarily selecting the mixing ratio of 3,5-triazine, a copolymer having an arbitrary composition ratio can be obtained.

In order to obtain a reaction product of cyanuric acid chloride and ethylenediamine, cyanuric acid chloride and ethylenediamine are mixed in a molar ratio of 2: 3 with an organic or inorganic base (eg triethylamine, tributylamine, ethylenediamine, sodium hydroxide, potassium hydroxide, Alternatively, the reaction is carried out using water as a solvent in the presence of sodium carbonate). The reaction is carried out starting from a temperature below 10 ° C. and slowly heating to the reflux temperature. After completion of the reaction, the reaction product is filtered to separate a solid matter, and the solid matter is washed with boiling water to remove a salt as a by-product, and then the solid matter is dried. The obtained reaction product was insoluble in an organic solvent, and its solubility in water at room temperature was 0.1% or less. The decomposition temperature is 32
4 ° C.

Suitable as the thermoplastic resin which is the component (C) used in the present invention are polyethylene resin, polypropylene resin, poly-1-butene resin, poly-4-methyl-
1-pentene resin, poly-1-hexene resin, poly-1
-One or more resins selected from octene resins and poly-1-decene resins or resin blends consisting of two or more thereof, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer ( AS resin). Further, suitable elastomers are olefin-based thermoplastic elastomers and styrene-based thermoplastic elastomers. Further, suitable polypropylene resin is crystalline propylene homopolymer, propylene and ethylene containing propylene as a main component, butene-1, pentene-1, hexene-1, 4-methylpentene-1, heptene-1,
It is a crystalline copolymer with one or more selected from octene-1 and decene-1, or a mixture of two or more thereof.

In the flame-retardant thermoplastic resin composition of the present invention, various additives which are usually added to the thermoplastic resin, such as antioxidants, UV inhibitors, antistatic agents, copper damage inhibitors, A lubricant, a neutralizing agent (a metal salt of stearic acid, hydrotalcite, manaceite, or the like), a pigment, or the like can be used in combination as appropriate.

The flame-retardant thermoplastic resin of the present invention can be produced, for example, by the following method. That is, the above-mentioned insoluble ammonium polyphosphate particles and the above-mentioned nitrogen-containing organic compound are charged into a thermoplastic resin into various stirring and mixing devices such as a Henschel mixer (trade name), a super mixer or a tumbler mixer, and then 1 to 10
The target flame-retardant composition can also be obtained by stirring and mixing for a minute, and the obtained mixture is melt-kneaded at a melt-kneading temperature of 170 to 220 ° C. using a roll kneader or a screw extruder and pelletized. You can get things.

【Example】

In order to specifically describe the present invention, examples and comparative examples are shown below, but the present invention is not limited thereto. The evaluations carried out in Examples and Comparative Examples were based on the following methods.

Flame Retardancy Evaluation UL Subject 94 (Underwriter Laboratories, Inc.)
Complies with the vertical combustion test specified in "Combustion test of plastic materials for parts of equipment". Thickness of test piece 1.6mm
(1/16 inch) Hot water immersion test evaluation Test piece (length 100 mm x width 100
mm × thickness 2 mm) was molded by an injection molding machine, and the surface electric resistance value of the test piece was measured by a vibration capacitance type micro-current / electrometer (Takeda Riken Kogyo Co., Ltd.). Then, the test piece was immersed in hot water at 95 ° C. for 2 hours and then taken out, and water drops adhering to the test piece were wiped off with a wiper paper to measure the surface electric resistance value of the test piece. If the surface electric resistance value was significantly reduced after hot water immersion, the bleeding resistance was poor. Evaluation of bleeding resistance retention days Test pieces (length 100 mm x width 100 mm x thickness 2 mm) were molded with an injection molding machine, and the surface electric resistance value of the test pieces was measured by a vibration capacitance type microcurrent potentiometer (Takeda Riken Industry Co., Ltd.).
It was measured at. Then, the test piece is subjected to a temperature of 80 ° C. and a humidity of 80%.
The sample was left to stand in a thermo-hygrostat regulated at 1, and taken out at each time. The taken-out test piece was dried for 2 hours in a thermostatic oven adjusted to a temperature of 80 ° C., and the surface electric resistance value of the test piece was measured. If the surface electrical resistance value of the test piece was significantly reduced after being taken out from the constant temperature and humidity chamber, it was determined that the bleeding resistance was poor under high temperature and high humidity conditions, and the surface electrical resistance value was high when exposed to high temperature and high humidity conditions. The number of days until it decreased was examined.

The insoluble ammonium polyphosphate used in the examples of the present invention was obtained by treating melamine-coated ammonium polyphosphate, and the melamine-coated ammonium polyphosphate was obtained by the following method. 280 ° C in advance
2000 parts of II type ammonium polyphosphate fine particles having an average particle diameter of 6.4 μm were put into the kneader heated to 1, and the mixture was heated and mixed for 3 hours under a nitrogen gas atmosphere or an inert gas atmosphere to desorb ammonia. 200 parts of melamine is added to powdery ammonium polyphosphate in a state where the amount of ammonia is less than the stoichiometric amount. At this point, the upper lid of the kneader is closed, and heating and mixing is performed at 280 ° C. for 4 hours in this state. The hot mixing was done without changing the morphology of the ammonium polyphosphate. Thus, 2100 parts of melamine-coated ammonium polyphosphate was obtained. As a result of observation with an electron microscope, it was confirmed that the particle surfaces of the type II ammonium polyphosphate microparticles were uniformly coated with melamine.

Further, the above-mentioned type II ammonium polyphosphate was obtained by the following method. A mixture of 660 g (5 mol) of diammonium phosphate and 710 g (5 mol) of phosphorus pentoxide was added to 5 liters heated to 290 to 300 ° C. in a table kneader while maintaining a nitrogen gas atmosphere, and the mixture was heated and stirred.
After 0 minutes, 195 g of 76.9% urea solution at 80 ° C. was added by spraying. 250 hours for 2.5 hours under ammonia atmosphere
Calcination was performed at ˜270 ° C. to obtain 1460 g of powdery ammonium polyphosphate. This ammonium polyphosphate had a mixture of single particles and a part of agglomerates, and was coarsely crushed in an ammonia atmosphere with a crusher (AP-B type manufactured by Hosokawa Micron) to separate the single particles. The crystal form by X-ray diffraction was type II, and the average particle size of the particles was 6.4 μm.

EXAMPLE 1 Melamine-coated ammonium polyphosphate 100 was added to a kneader having an internal volume of 5 liters equipped with a heating and kneading mechanism and a deaeration mechanism.
0 g and 203 g of formalin having a concentration of 37% were added and mixed at room temperature for 30 minutes, then heated to 100 ° C. and mixed for 1 hour. In this way, the melamine present on the surface of the melamine-coated ammonium polyphosphate particles is crosslinked by the aldehyde group to form an insoluble ammonium polyphosphate (A
1) 1035 g was obtained. 20% by weight of this insoluble ammonium polyphosphate (A1) was used as a nitrogen-containing organic compound.
-10% by weight of homopolymer (B1) containing piperazinylene-4-morpholino-1,3,5-triazine as a monomer unit, and a crystalline propylene-ethylene block copolymer (ethylene content 8. 5% by weight, MFR (temperature 230 ° C, load 2.16 Kgf) 20
g / 10 min) 69.5% by weight, as various additives, 2,6-di-t-butyl-p-cresol 0.2% by weight, dimyristyl-β, β′-thiodipropionate 0.2% by weight, 0.1% by weight of calcium stearate was charged into a Henschel mixer (trade name) and stirred and mixed for 3 minutes. The obtained mixture was melt-kneaded (temperature 200 ° C.) using an extruder (diameter 30 mm) and then extruded to obtain pellets of a flame-retardant composition. After drying the obtained pellets at a temperature of 100 ° C. for 3 hours, the pellets were made into predetermined test pieces using an injection molding machine (the maximum temperature of the cylinder was set to 220 ° C.), and the flame resistance and heat A water immersion test and evaluation of bleeding resistance were conducted and shown in Table 1. Examples 2 to 4 In Example 2, as a nitrogen-containing organic compound, 2-piperazinylene-4-N, N-bis (hydroxyethyl) amino-
A homopolymer (B2) containing 1,3,5-triazine as a monomer unit was prepared in Example 3 from 2-piperazinylene-4-morpholino-1,3,5-triazine and 2-piperazinylene-4-N, N-. Bis (hydroxyethyl) amino-
The reaction product (B4) obtained by reacting a copolymer (B3) having a 1,3,5-triazine component molar ratio of 1: 1 with Example 4 in which cyanuric chloride and ethylenediamine were reacted at a molar ratio of 2: 3. Was melt-kneaded and extruded to obtain pellets in the same manner as in Example 1 except that Predetermined test pieces were prepared using the obtained pellets, and flame retardancy, hot water immersion test and bleed resistance were evaluated. The results are shown in Table 1. Example 5 Melamine-coated ammonium polyphosphate 10 was added to a flask having an internal volume of 5 liters equipped with a heating and stirring mechanism and a reflux mechanism.
00 g and 900 g of toluene are added. Next, 132 g of hexamethylene diisocyanate and 2.6 g of Nikka octic tin catalyst are added and mixed at room temperature. Next, the temperature was raised to the reflux temperature, the mixture was heated and mixed for 2 hours, cooled, filtered, and dried in a dryer at 100 ° C. for 1 hour. In this way, 1080 g of insoluble ammonium polyphosphate (A2) in which melamine existing on the surface of the melamine-coated ammonium polyphosphate particles was crosslinked with an isocyanate group was obtained. Melt-kneading and extrusion were carried out in accordance with Example 1 except that the insoluble ammonium polyphosphate (A2) was adjusted to 20% by weight to obtain pellets. Predetermined test pieces were prepared using the obtained pellets, and flame retardancy, hot water immersion test and bleed resistance were evaluated. The results are shown in Table 1. Example 6 A melamine-coated ammonium polyphosphate 10 was added to a flask having an internal volume of 5 liters equipped with a heating and stirring mechanism and a reflux mechanism.
After adding 00 g, 909 g of water and 91 g of methanol, 92 g of 49% concentration glyoxal is added and mixed at room temperature. Then, the temperature is raised to the reflux temperature and the mixture is stirred for 2 hours. After cooling, it is filtered and dried in a dryer at 100 ° C. for 1 hour. In this way, the insoluble ammonium polyphosphate (A3) 1025 in which the melamine existing on the surface of the melamine-coated ammonium polyphosphate particles is crosslinked by the aldehyde group
g was obtained. This insoluble ammonium polyphosphate (A3)
Was melt-kneaded and extruded in the same manner as in Example 1 except that the content was 20% by weight to obtain pellets. Predetermined test pieces were prepared using the obtained pellets, and flame retardancy, hot water immersion test and bleed resistance were evaluated. The results are shown in Table 1. Example 7 66.5% by weight of low-density polyethylene (Petrosene 186, manufactured by Tosoh Corporation) as a thermoplastic resin, 24% by weight of insoluble ammonium polyphosphate (A1), and 2-piperazinylene-4-morpholino-as a nitrogen-containing organic compound. 1,
9% by weight of a homopolymer (B1) containing 3,5-triazine as a monomer unit, and 2,6-di-t-as various additives.
Butyl-p-cresol 0.2% by weight, dimyristyl-
Melt-kneading and extrusion were carried out in accordance with Example 1 except that the content of β, β′-thiodipropionate was 0.2% by weight and that of calcium stearate was 0.1% by weight, to obtain pellets. Predetermined test pieces were prepared using the obtained pellets, and flame retardancy, hot water immersion test and bleed resistance were evaluated. The results are shown in Table 1. Example 8 As a thermoplastic resin, a polystyrene resin (Stylon 4
75S Asahi Kasei Corporation 63.5% by weight, insoluble ammonium polyphosphate (A1) 26% by weight, 2-piperazinylene-4-morpholino-1, as a nitrogen-containing organic compound,
10% by weight of a homopolymer (B1) containing 3,5-triazine as a monomer unit, and 2,6-di-t as various additives.
-Butyl-p-cresol 0.2 wt%, dimyristyl-β, β'-thiodipropionate 0.2 wt%, calcium stearate 0.1 wt% Example 1
Melt-kneading and extrusion were carried out in accordance with to obtain pellets. Predetermined test pieces were prepared using the obtained pellets, and flame retardancy, hot water immersion test and bleed resistance were evaluated. The results are shown in Table 1. Comparative Example 1 Pellets were obtained by melt-kneading and extruding in accordance with Example 1 except that insoluble ammonium polyphosphate was replaced with 20% by weight of II type ammonium polyphosphate fine particles (A4).
Predetermined test pieces were prepared using the obtained pellets, and flame retardancy, hot water immersion test and bleed resistance were evaluated.
The results are shown in Table 1. Comparative Example 2 Melt kneading according to Example 1 except that ammonium polyphosphate ((Sumisafe-P (trademark, manufactured by Sumitomo Chemical Co., Ltd.), (A5)) 20 wt% was used instead of insoluble ammonium polyphosphate. The pellets were extruded to obtain pellets.
A hot water immersion test and evaluation of bleed resistance were performed. The results are shown in Table 1. Comparative Example 3 In a flask having an internal volume of 5 liter equipped with a heating and stirring mechanism and a reflux mechanism, 900 g of ammonium type II polyphosphate and 6 parts of water were added.
A mixed solvent of 00 g / methanol 400 g is added, and the mixture is stirred and mixed at room temperature. Next, a separately prepared methylol melamine solution (formalin 160 g with 37% concentration in 100 g melamine)
Was added and stirred at 70 ° C. for 1 hour) and PH was added.
It was adjusted to 5 and reacted at 75 ° C. for 2 hours to make methylolmelamine into a resin. After cooling, it was filtered and dried in a dryer at 100 ° C. for 1 hour. In this way, 1030 g of ammonium polyphosphate (A6) in which a melamine resin was attached to the surface of type II ammonium polyphosphate was obtained. Melamine resin-attached ammonium polyphosphate (A6) thus obtained
Pellets were obtained by melt-kneading and extruding according to Example 1 except that 20% by weight was used instead of insoluble ammonium polyphosphate. Predetermined test pieces were prepared using the obtained pellets, and flame retardancy, hot water immersion test and bleed resistance were evaluated. The results are shown in Table 1.

As is apparent from Table 1, it is understood that the blending of insoluble ammonium polyphosphate significantly improves the bleeding property under high temperature and high humidity conditions.

【The invention's effect】

The flame-retardant thermoplastic resin composition of the present invention has a crosslinked structure formed by a compound having a functional group capable of reacting the active hydrogen of the melamine molecule added or attached to the surface of ammonium polyphosphate. Since insoluble ammonium polyphosphate is used, no bleeding occurs even under high temperature and high humidity conditions. Moreover, the flame retardancy of the molded product is excellent, and no decomposition gas is generated during the molding process. Therefore, it can be suitably used in the field of various molded products used under high temperature and high humidity conditions, for example, in the field of electric appliances.

[0026]

[Table 1]

Claims (7)

[Claims] 1. A flame-retardant thermoplastic resin composition comprising the following components (A), (B), and (C) in a total amount of 100% by weight: (A) coating of melamine-coated ammonium polyphosphate particles. Insoluble ammonium polyphosphate particles characterized in that the surface of the particle is cross-linked by active hydrogen belonging to an amino group in a melamine molecule existing in a layer and a compound having a functional group capable of reacting with the active hydrogen: 10 -40 wt% (B) Nitrogen-containing organic compound: 1-20 wt% (C) Thermoplastic resin: 89-40 wt% 2. The compound having a functional group capable of reacting with active hydrogen belonging to an amino group in a melamine molecule is a compound having an isocyanate group, a glycidyl group, a carboxyl group, a methylol group or an aldehyde group. Flame-retardant thermoplastic resin composition. 3. The flame-retardant thermoplastic resin composition according to claim 1, wherein the number of functional groups of the compound having a functional group capable of reacting with active hydrogen belonging to the amino group in the melamine molecule is 1 or 2 or more. . 4. The flame-retardant heat according to claim 1, wherein the melamine-coated ammonium polyphosphate is a melamine-coated ammonium polyphosphate obtained by coating powdery ammonium polyphosphate with 0.5 to 20% by weight of melamine. Plastic resin composition 5. The flame-retardant thermoplastic resin composition according to claim 1, wherein the nitrogen-containing organic compound is a homopolymer and / or a copolymer containing a monomer having a structure represented by the following chemical formula 1 as a basic unit. Chemical 1] (Wherein X and Z ¹ are both structures bonded to a triazine skeleton through a nitrogen atom, and X is an alkylamino group or a morpholino group represented by a group of —NHR ¹ or —NR ² R ³ , It is a piperidino group and R ¹ , R ² and R ³ are linear or branched alkyl groups having 1 to 6 carbon atoms (R ² and R ³ may be the same or different). Alternatively, X is a hydroxyalkylamino group represented by the group —NHR ⁴ —NR ⁵ R ⁶ and R ⁴ , R ⁵ and R ⁶ have 2 carbon atoms.
A linear or branched hydroxyalkyl group having 6 to 6 (R ⁵ and R ⁶ may be the same or different). Z ¹ is a divalent group of piperazine, or is of the formula —HN
(CH ₂₎ 2 divalent group represented by MNH- (the m is an integer from 2 to 6), or -NR ⁷ (CH ₂₎ a _l R ⁸ N-a group represented by R ^7, R One or both of ⁸ is a hydroxyethyl group. ) 6. The flame-retardant thermoplastic resin composition according to claim 1, wherein the nitrogen-containing organic compound is a reaction product obtained by reacting cyanuric chloride with a diamine. 7. The flame-retardant thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is an aliphatic thermoplastic resin, an aromatic thermoplastic resin, an elastomer thereof or a mixture of two or more thereof.