JPH08183876A - Flame-retardant thermoplastic polymer composition - Google Patents

Abstract

PURPOSE: To obtain a flame-retardant thermoplastic polymer composition improved in flame retardancy and bleeding resistance by mixing a solid oxygenous compound of a specified element with an organic nitrogenous compound, water- insoluble ammonium polyphosphate and a thermoplastic polymer. CONSTITUTION: Melamine-coated ammonium polyphosphate particles prepared by chemically adding and/or adhering sublimed melamine to the surfaces of ammonium polyphosphate particles are reacted with a crosslinking compound having a functional group reactive with the active hydrogen atom of the amino groups of melamine to obtain water-insoluble ammonium polyphosphate. 0.1-5wt.% solid oxygenous compound of an element of any one of groups II-IV in the periodic table is mixed with 1-20wt.% organic nitrogenous compound represented by the formula [wherein X is -NHR<1> , -NHR<2> R<3> or the like (wherein R<1> to R<3> are each 2-6 linear or branched alkyl); and Z<1> is a bivalent group of piperazine or the like], 10-40wt.% above water-insoluble ammonium polyphosphate and 88.9-35wt.% thermoplastic polymer selected from among aliphatic and aromatic thermoplastic resins, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic polymer composition having excellent flame retardancy. For details, see Periodic Table II, III
Oxygen-containing solid compound (A) of group III or group IV element, nitrogen-containing organic compound (B), water-insoluble ammonium polyphosphate particles (C) obtained by coating ammonium polyphosphate with a coating layer having a melamine cross-linking structure, and thermoplasticity The present invention relates to a thermoplastic polymer composition which contains the polymer (D) in a specific amount and has excellent flame retardancy.

[0002]

2. Description of the Related Art Conventionally, thermoplastic polymers have been used in the fields of industrial and household electric appliances by taking advantage of their hygienic properties, processability, chemical resistance, weather resistance, electrical characteristics and mechanical strength. It has been widely used in various fields such as construction, upholstery, and automobile parts, and the applications in which the thermoplastic polymer is used are also expanding. With the expansion of such applications, flame retardancy is also required of the thermoplastic polymer, and the required performance is becoming severer year by year.
Particularly recently, a flame-retardant resin composition prepared by blending a halogen-containing compound and antimony oxide, which are the mainstream of conventional flame-retarding technology, into a thermoplastic polymer is capable of generating a halogen-based gas during combustion or molding. Is considered a problem. Therefore, there is a demand for flame-retardant resin compositions that do not generate these halogen-based gases during combustion or molding.

In order to meet these demands, in recent research, a specific metal hydrate capable of suppressing the combustion of resin by causing decomposition and dehydration reaction by endothermic reaction at the combustion temperature of resin is blended as an inorganic flame retardant. Measures have been proposed. However, in this case, in order to obtain the target flame-retardant resin composition, it is necessary to add a large amount of the metal hydrate in order to compensate for the extremely weak flame-retarding effect.
As a result, in addition to the molding processability of the obtained flame-retardant resin composition being reduced, various properties such as mechanical strength of the molded article obtained from the composition are also reduced. Therefore, in order to ameliorate the problems caused by the above-mentioned large amount of compounding, further compounding of an inorganic compound has been proposed.

For example, blending of molybdenum or a molybdenum compound (JP-A-1-268738) and blending of whisker-like silicon carbide (JP-A-3-9937).
There is. However, flame-retardant resin compositions prepared by adding other inorganic compounds to these metal hydrates cannot solve the problems associated with a large amount of compound, and achieve the desired flame retardancy. However, the above-mentioned problems in terms of work have not been fundamentally resolved.

Another recent proposal is ammonium polyphosphate and a nitrogen-containing organic compound, which produces a nonflammable gas (water, carbon dioxide, ammonia, nitrogen, etc.) and a carbonaceous residue by thermal decomposition. A flame-retardant resin composition containing a combination of the above nitrogen-containing organic compounds is found.

For example, a flame-retardant composition comprising a polymer or oligomer of a 1,3,5-triazine derivative and ammonium polyphosphate has been proposed. (JP-A-59-
147050, EP-0475418).
However, the flame-retardant resin composition prepared by combining the above-mentioned ammonium polyphosphate and the nitrogen-containing organic compound is lower in composition (smaller composition) than the flame-retardant resin composition mainly composed of metal hydrate. It exhibits high flame retardancy, but its flame retardancy is not yet sufficient.

Further, while the above flame-retardant composition exhibits a high flame-retardant effect, a molded article obtained by using the composition has a polyphosphoric acid on its surface under high temperature and high humidity conditions such as in the rainy season. The phenomenon that ammonium bleeds violently occurs. Its cause is sought due to its hygroscopicity, water-solubility and its extreme hydrolytic susceptibility due to the chemical structure of ammonium polyphosphate.

Various studies have been conducted to improve the hydrolysis stability of ammonium polyphosphate. JP-B-53-15478 and JP-B-52-39930 disclose a method for obtaining a hydrolysis-stable ammonium polyphosphate by reacting a water-insoluble melamine, but the hydrolysis of the ammonium polyphosphate is disclosed. Stability is not yet sufficient.

Further, Japanese Patent Laid-Open No. 61-103962 discloses a method for producing a hydrolytically stable granular flame retardant by curing ammonium polyphosphate and a melamine / formaldehyde resin in a suspension. There is. However, when the resin component is cured in the suspension, the particles agglomerate with each other, which causes an increase in the particle size. Therefore, when such a granular flame-retardant agent is added to a thermoplastic polymer as one component of a flame retardant, it has a drawback that the mechanical strength of the obtained product is lowered.

[0010]

DISCLOSURE OF THE INVENTION The present invention is a flame retardant which has a low content of a flame retardant and is excellent in flame retardancy, and is also excellent in bleed resistance and which hardly causes a bleed phenomenon even in a high temperature and high humidity atmosphere. To provide a volatile polymer composition. That is, the present inventors have earnestly studied to obtain a flame-retardant thermoplastic polymer composition that exhibits high flame retardancy even with a low content of a flame retardant, and that also has high bleed resistance. went. As a result, a periodic table for a flame retardant composition composed of a water-insoluble ammonium polyphosphate, particularly a water-insoluble ammonium polyphosphate obtained by coating ammonium polyphosphate particles with a coating layer having a melamine crosslinked structure and a nitrogen-containing organic compound. Of II, by adding a small amount of oxygen-containing solid compounds of elements classified into III or IV, found that the above problems can be solved, further as a result of further studies based on this finding, the present invention completed.

[0011]

The flame-retardant thermoplastic polymer according to the present invention comprises the following components (A), (B), (C) and (D), and their total amount is 100% by weight. (A) 0.1 to 5% by weight, preferably 0.5 to 0.5% by weight of an oxygen-containing solid compound of an element belonging to Group II, Group III or Group IV of the periodic table.
˜2 wt%, (B) nitrogen-containing organic compound 1 to 20 wt%,
Preferably 3 to 18% by weight, (C) water insoluble ammonium polyphosphate 10 to 40% by weight, preferably 15 to 26
% And (D) thermoplastic polymer 88.9 to 35% by weight, preferably 81.5 to 54% by weight.

In the present invention, the elements belonging to Group II, Group III or Group IV of the periodic table contained in the oxygen-containing solid compound are Ca, Ba, Sr, Mg, Al, Si, Zn and C.
Examples thereof include d, Ti, Zr and Sn. These may be used alone or in combination of two or more.

Examples of the oxygen-containing solid compound used in the present invention include hydroxides, basic carbonates, carbonates, carbonate hydrates, silicates and silicate hydrates of the elements belonging to the above-mentioned groups II to IV. , Oxides and oxide hydrates, and complex oxides, complex salts and complex salt hydrates of two or more elements belonging to the above-mentioned groups II to IV. These may be used alone or in combination of two or more. The average particle size of such oxygen-containing solid compound is preferably 10 μm or less.

The water-insoluble ammonium polyphosphate used in the present invention includes, in particular, ammonium polyphosphate particles and a coating layer for coating the surface of the particles, the coating layer containing melamine and amino groups of the melamine. A cross-linked melamine-coated ammonium polyphosphate particle having a cross-linked structure formed by the reaction of a cross-linking compound having a functional group capable of reacting with the active hydrogen to be formed can be exemplified.

The cross-linking compound may be a monofunctional or polyfunctional compound having a functional group capable of reacting with active hydrogen belonging to the amino group of melamine, and the functional group may be, for example, an isocyanate group or a glycidyl group. , A carboxyl group, a methylol group and an aldehyde group. When the cross-linking compound is polyfunctional, these groups may be a single group or a combination of two or more types.

In the crosslinked melamine-coated ammonium polyphosphate used in the present invention, the coating layer is, for example, 0.5 to 2 with respect to the surface of the powdery ammonium polyphosphate.
It is obtained by adding and / or depositing 0% by weight of sublimed melamine and then reacting this melamine with a crosslinking compound.

Examples of the nitrogen-containing organic compound used in the present invention include homopolymers and / or copolymers having a monomer of the structure represented by the general formula [I] as a basic unit.

[0018]

Embedded image

[Wherein X represents the formula: --NHR ¹ , --NR ²
R ^3, -NHR ⁴ or -NR ⁵ R ⁶ (wherein, R ^1, R ² and R
³ is a linear or branched alkyl group having 2 to 6 carbon atoms, R ² and R ³ may be the same or different, may be bonded to each other to form a ring, R ⁴ , R ⁵ and R ⁶ are
A linear or branched hydroxyalkyl group having 2 to 6 carbon atoms, R ⁵ and R ⁶ may be the same or different, and may be bonded to each other to form a ring). Z ¹ is a divalent group of piperazine, represented by the formula: —HN
(CH ₂₎ 2 divalent radical (wherein represented by mNH-, m is 2
Is a number of 6), or _{^{Formula: -NR 7 (CH 2) l}} R 8 N-
(In the formula, one or both of R ⁷ and R ⁸ is a hydroxyethyl group, and 1 is a number of 2 to 6). As such a nitrogen-containing organic compound, a reaction product obtained by reacting cyanuric acid chloride and a diamine is particularly mentioned.

The thermoplastic polymer used in the present invention includes at least one elastomer selected from aliphatic thermoplastic resins; aromatic thermoplastic resins; aliphatic elastomers and aromatic elastomers. ; And 1
Examples of the thermoplastic elastomer include one or more thermoplastic resins and one or more elastomers or partially crosslinked elastomers.

More specifically, examples of the thermoplastic polymer include the following thermoplastic resins. (1) Polyolefin resin; (2) Polystyrene resin; (3) Acrylic resin; (4) Polyvinyl resin; (5) Nylon (polyamide resin); (6) Thermoplastic polyester resin; (7) Aromatic resin Compound homopolymers and copolymers; (8) Thermoplastic 1-olefin copolymer elastomers; (9) Conjugated diene homopolymer rubbers and copolymer rubbers;
And (10) condensation polymerization elastomer.

These thermoplastic resins (1) to (10) may be used alone or in combination of two or more kinds. Furthermore, more specifically, examples of the thermoplastic polymer include the following polymers. (1) Polyethylene resin, polypropylene resin, poly 1
-Butene resin, poly-4-methyl-1-pentene resin,
Poly 1-hexene resin, poly 1-octene resin and poly 1-decene resin; (2) Polystyrene resin (PS), high impact polystyrene resin (HIPS), heat resistant polystyrene resin (styrene-α-methylstyrene copolymer) Resin), acrylonitrile-styrene resin (AS) and acrylonitrile-butadiene-styrene resin (ABS); (3) polymethyl acrylate and polymethyl (meth)
Acrylate; (4) Polyvinyl chloride resin and polyvinylidene chloride resin; (5) 6-nylon, 7-nylon, 11-nylon,
12-nylon, 6,6-nylon, 6,7-nylon, 6,10-nylon, 6,12-nylon, a condensate of a terephthalic acid unit and a p-phenylenediamine unit,
m-xylylene-adipic acid condensed nylon (MXD
6), 6- / 6,6-co-condensed nylon and 6- / 12-
(6) Polyethylene terephthalate, polybutylene terephthalate and polyphenylene terephthalate; (7) Polycarbonate resin (PC), polysulfone resin and polyphenylene ether resin (PPE), and polyurethane resin (PU); (8) Ethylene-propylene copolymer Polymerized elastomer (EP
M), ethylene-propylene-non-conjugated diene copolymer elastomer (EPDM), ethylene-propylene-2-ethylidene-5-norbornene copolymer elastomer (EP
DM) and propylene-1-butene copolymer elastomer (PBM); (9) poly-1,3-butadiene rubber (BR), polyisoprene rubber (IR), acrylonitrile-1.3-butadiene copolymer rubber (NBR). , Chloroprene rubber, isobutene-isoprene rubber (IIR: commonly called "butyl rubber"), natural rubber (NR); and (10) polyurethane elastomer.

These resins (1) to (10) may be used alone or in combination of two or more. BEST MODE FOR CARRYING OUT THE INVENTION As described above, the flame-retardant thermoplastic resin composition according to the present invention has a specific amount of oxygen-containing solid compound (A), nitrogen-containing organic compound (B), water-insoluble ammonium polyphosphate. It contains (C) and a thermoplastic polymer (D). Hereinafter, each sentence (A) to (D) will be described in more detail.

Oxygen-containing solid compound (A) Group II, III of the periodic table used in the flame-retardant composition of the present invention
Oxygen-containing solid compound (A) of elements belonging to Group IV or IV
Is a water-insoluble ammonium polyphosphate and a nitrogen-containing organic compound to be blended in a base material made of a thermoplastic polymer,
When added in a small amount, the flame retardancy of the resulting resin composition is significantly improved.

The elements belonging to Group II to Group IV of the periodic table are, specifically, Ca, Ba, Sr, Mg, Al and S.
Examples thereof include i, Zn, Cd, Ti, Zr and Sn.
Oxygen-containing solid compounds used in the present invention are these II
Hydroxides, basic carbonates, carbonates, carbonate hydrates, silicates, hydrates of silicates, oxides and oxide hydrates, etc. of Group I to Group IV elements, or Group II to Group II It may be a complex oxide of two or more kinds of group IV elements, a complex oxide hydrate, a complex salt and a complex salt hydrate.

These oxygen-containing solid compounds may be used alone or in combination of two or more. As such an oxygen-containing solid compound, specifically, calcium hydroxide, barium hydroxide, magnesium hydroxide, basic magnesium carbonate, basic zinc carbonate, calcium silicate hydrate, magnesium oxide hydrate, Aluminum hydroxide, aluminum oxide hydrate and titanium oxide hydrate, and hydrotalcite (Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂
O), kaolinite (Al ₂ O ₃・ 2SiO ₂・ 2H
₂ O), sericite (K ₂ O / 3Al ₂ O ₃ / 6SiO ₂
2H ₂ O), pyrophyllite (Al ₂ O ₃・ 4SiO ₂・
H ₂ O), bentonite (Al ₂ O ₃・ 4SiO ₂・ 2H ₂
O), talc (3MgO.4SiO ₂ .H ₂ O) and the like.

The above-mentioned oxygen-containing solid compound (A) is preferably in the form of powder and has an average particle size of 10 μm or less.
It is 5% by weight, preferably 0.5-2% by weight. When the blending amount is 0.05% by weight or less, sufficient improvement in flame retardancy cannot be obtained, and when the blending amount is 7% by weight or more, the flame retardancy imparting effect is significantly reduced.

Nitrogen-Containing Organic Compound (B) The nitrogen-containing organic compound (B) used in the flame-retardant composition of the present invention, when present in the thermoplastic polymer together with the powdery ammonium polyphosphate, causes ignition or flame contact. It is an organic compound that produces non-flammable gas (water, carbon dioxide, ammonia, nitrogen, etc.) due to thermal decomposition caused by the above, and almost only carbonaceous residue remains. Examples of such a nitrogen-containing organic compound include, for example, a homopolymer consisting of one kind selected from the structural units represented by the general formula [I] and /
Alternatively, there may be mentioned a copolymer composed of two or more kinds.
Examples of such a constitutional unit include the constitutional unit exemplified in the following [1]. [1] 2-piperazinylene-4-morpholino-1,3,3
5-triazine, 2-piperazinylene-4-piperidino-1,3,5-triazine, 2-piperazinylene-4-
N, N'-bis (2-hydroxyethyl) amino-1,
3,5-triazine, 2-piperazinylene-4-N-
(2-Hydroxyethyl) amino-1,3,5-triazine.

The nitrogen-containing organic compound (B) is [2]
It may be a product obtained by reacting cyanuric chloride with a diamine. Such nitrogen-containing organic compound is preferably (i) a product obtained by the reaction of cyanuric chloride and a diamine at a molar ratio (former / latter =) 2/3; (ii) cyanuric chloride The product obtained by the reaction with ethylenediamine in a molar ratio (former / latter =) 2/3; and (iii) cyanuric chloride and 1,3-diaminopropane in a molar ratio (former / latter =) 2/3. The reaction product obtained by the reaction can be exemplified.

In the present invention, together with such a nitrogen-containing organic compound (B), a known nitrogen-containing organic compound, for example, one or more groups> C = 0,> C = S or> NH incorporated in a cyclic structure is added. Reaction product of contained heterocyclic nitrogen compound and aldehyde; reaction product of benzylguanamine and aldehyde; or tris (2-hydroxyethyl) isocyanurate, tris (3-hydroxy-N-propyl) isocyanurate, tris ( A nitrogen-containing organic compound which is a derivative of isocyanuric acid such as 2,3-epoxypropyl) isocyanurate can also be used in combination.

<Production Method of Triazine Monomer> Here, a production method of the nitrogen-containing organic compound represented by the above formula [I] will be described. That is, for example, the above-mentioned 2-piperazinylene-4-morpholino-which is one of nitrogen-containing organic compounds.
To obtain a homopolymer having 1,3,5-triazine (a structural unit in which X is a morpholino group and Z is piperazinylline in the general formula [I]) as a structural unit, the following operation may be performed.

An equimolar amount of 2,6-dihalo-4-morpholino-1,3,5-triazine (eg 2,6-dichloro-
4-morpholino-1,3,5-triazine or 2,6-
Dibromo-4-morpholino-1,3,5-triazine)
And piperazine are reacted in the presence of an organic base or an inorganic base (eg, triethylamine, tributylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, etc.) in an inert solvent such as xylene under heating. After completion of the reaction, the reaction compound is filtered to separate and collect 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 resulting homopolymer having 2-piperazinylene-4-morpholino-1,3,5-triazine as a constituent unit is insoluble in ordinary organic solvents, its melting point is not observed, and its decomposition temperature is about 304 ° C. The true density was 1.3 g / cc.

Further, 2-piperazinylene-4-bis (hydroxyethyl) amino-1,3,5-triazine is a structural unit (in the general formula [I], X is a bis (hydroxyethyl) amino group and Z is a piperazinylene group. The same method as described above can also be applied to the case of obtaining a homopolymer of (2) using 2,6-dihalo-4-bis (hydroxyethyl) amino-1,3,5-triazine as a raw material.

Further, 2-piperazinylene-4-morpholino-1,3,5-triazine and 2-piperazinylene-
To obtain a copolymer having 4-bis (hydroxyethyl) amino-1,3,5-triazine as a constitutional unit, 2,6-dihalo-4-morpholino-1,3,5-triazine and 2,6-dihalo-4-morpholino-1,3,5-triazine
6-dihalo-4-bis (hydroxyethyl) amino-1,
The same method as described above can be applied using a mixture of 3,5-triazine as a raw material. 2,6-Dihalo-4-morpholino-1,3,5-triazine and 2,6-dihalo-
4-bis (2-hydroxyethyl) amino-1,3,5
-A copolymer having an arbitrary composition ratio can be obtained by arbitrarily selecting the mixing ratio of triazine.

In order to obtain the reaction product of cyanuric acid chloride and ethylenediamine, cyanuric acid chloride and ethylenediamine are mixed with the organic or inorganic base (eg, triethylamine, tributylamine, water) in a molar ratio of (former / latter =) 2/3. The reaction is carried out using water as a solvent in the presence of sodium oxide, potassium hydroxide, sodium carbonate or the like. The reaction is started at a temperature of 10 ° C. or lower and gradually heated to the reflux temperature of the solvent. After the 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 by-product salt, and the solid matter remaining is dried. The obtained solid reaction product is insoluble in an organic solvent, the solubility in water at room temperature is 0.1% or less, and the decomposition temperature is 324.
° C.

The amount of the above-mentioned nitrogen-containing organic compound (B) is usually 1 to 20% by weight, preferably 3 to 1% by weight based on the composition.
8% by weight. When the blending amount is 0.5% by weight or less, sufficient flame retardancy is not imparted, and even when the blending amount is 25% by weight or more, flame retardancy exceeding it is hardly exhibited.

Water-insoluble ammonium polyphosphate (C) As the water-insoluble ammonium polyphosphate (C) used in the present invention, particularly ammonium polyphosphate particles,
A coating layer for coating the surface of the particles, and the coating layer is crosslinked between melamine molecules by reacting with a crosslinking compound having a functional group capable of reacting with active hydrogen belonging to the amino group of melamine. Examples thereof include crosslinked melamine-coated ammonium polyphosphate particles having a crosslinked structure in which groups are interposed.

Such crosslinked melamine-coated ammonium polyphosphate is prepared by preparing melamine-coated ammonium polyphosphate particles in which sublimated melamine is added and / or attached to the surface of the ammonium polyphosphate particles, and then the melamine-coated ammonium polyphosphate particles are reacted with a crosslinking compound. It can be obtained by crosslinking melamine on the grain surface.

As the ammonium polyphosphate used for preparing the melamine-coated ammonium polyphosphate before crosslinking, a commercially available product may be used. Examples of the commercially available product include TERRAJU S10 (trademark, manufactured by Chisso Corporation), TERRAJU S20 (trademark, manufactured by Chisso Corporation), Sumisafe-P (trademark, manufactured by Sumitomo Chemical Co., Ltd.), Exorit-
422 (trademark, manufactured by Hoechst), Exolit-700
(Trademark, manufactured by Hoechst), Foscheck P / 40 (trademark, manufactured by Monsanto), and the like.

The melamine used may be a commercially available melamine monomer. Also,
For the preparation of the melamine-coated ammonium polyphosphate before crosslinking, it is preferable to use ammonium polyphosphate in which the amount of ammonia bound is less than the stoichiometric amount (hereinafter, referred to as ammonia-deficient ammonium polyphosphate).

Ammonia-deficient ammonium polyphosphate is prepared by heating ammonium polyphosphate particles in a heating and kneading apparatus such as a kneader without melting the ammonium polyphosphate particles and easily removing ammonia in the ammonium polyphosphate. Temperature at which desorption occurs, eg 3
00 ° C or less, preferably 0.5 at 200 to 300 ° C
It can be prepared by subjecting to a heat treatment for 5 hours to remove a part of the ammonia (5 to 10% by weight based on the stoichiometric amount of ammonia) originally present in the ammonium polyphosphate in a stoichiometric amount. The ammonia-deficient ammonium polyphosphate can also be prepared by selecting conditions such that the binding amount of ammonia is less than the stoichiometric amount in the known production process of ammonium polyphosphate.

The melamine-coated ammonium polyphosphate is
In the same apparatus used to prepare the ammonia-deficient ammonium polyphosphate, the melamine is heated to a temperature at which the ammonia-deficient ammonium polyphosphate particles do not melt and to a temperature at which melamine can sublime, that is, a temperature of 250 to 300 ° C. It can be prepared by adding and / or adhering the melamine to the hydroxyl group which has been added and the ammonia on the surface of the ammonium-deficient ammonium polyphosphate particles is desorbed to become an acid.

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, preferably 2 to 10% by weight, based on the ammonium polyphosphate, and in this method, the total amount of added melamine is added to ammonium polyphosphate and / or Deposition results in a melamine-coated ammonium polyphosphate.

The melamine-coated ammonium polyphosphate thus prepared is then reacted with a crosslinking compound having one or more functional groups capable of reacting with the active hydrogen forming the amino group of melamine.

The functional group capable of reacting with active hydrogen forming an amino group of melamine contained in such a cross-linking compound includes an isocyanate group, a glycidyl group, a carboxyl group, a methylol group and an aldehyde group. You can Examples of the cross-linking compound containing one or more such functional groups include isocyanate group-containing compounds, specifically, 1,6-diisocyanate hexane, 1,1-dimethylene bis (4-isocyanate benzene), 3,3-Dimethyldiphenyl-4,4-diisocyanate and 1,5-diisocyanate naphthalate, etc .; methylol group-containing compounds, specifically, methylol urea, methylol melamine, trimethylol ethane, trimethylol propane, etc .; aldehyde group containing Compound,
Specific examples thereof include formaldehyde, malonic aldehyde, glyoxal, and the like; and epoxy group-containing compounds, specifically, ethylene glycol diglycidyl ether, glycerol polyglycidyl ether, and the like. All of these are commercially available products.

The amount of such a crosslinking group used is 0.5 to 6 molar equivalent times, preferably 1 to 6 times the melamine molecule contained in the melamine-coated ammonium polyphosphate before crosslinking.
It is the equivalent amount of the functional group that is 3 molar equivalents. If the amount used is less than 0.5 molar equivalent times, it is difficult to form a sufficient crosslinked structure in the melamine coating layer, and therefore improvement in hydrolysis stability cannot be expected. On the other hand, when the amount is more than 6 molar equivalents, the unfavorable result that unreacted substances remain is generated.

The reaction of such a crosslinking compound with the melamine-coated ammonium polyphosphate can be carried out as follows. That is, a solution of a melamine-coated ammonium polyphosphate in a reactor having a function of heating stirring or kneading, and a crosslinking compound dissolved in a suitable solvent, for example,
Add an aqueous solution containing formaldehyde and mix. Then, the temperature at which active hydrogen forming the amino group of melamine and the cross-linking compound react to easily form a cross-linking structure, 80
To 200 ° C., preferably 100 to 150 ° C., the temperature is raised and the reaction is carried out for 0.5 to 2 hours. As a result, water-insoluble ammonium polyphosphate in which a crosslinked structure is formed in the melamine-coated ammonium polyphosphate is formed. To generate.

In this method, since the cross-linking reaction is carried out using a mono-molecular cross-linking agent, the cross-linking reaction of the melamine-coated ammonium polyphosphate particles on the same particle is prioritized and different through the cross-linking agent. It does not cause agglomeration of particles. The reaction can proceed in a solvent system or a non-solvent system, and as the solvent system, either a single solvent system consisting of water and / or an organic solvent or a mixed solvent system can be used.

The amount of such water-insoluble ammonium polyphosphate (C) to be compounded is 10 to 40% by weight, preferably 15 to 26% by weight, based on the composition. The blending amount is 7% by weight
Hereinafter, in detail, if it is 5% by weight or less, sufficient flame retardancy cannot be obtained, and even if it is compounded in 50% by weight, specifically 45% by weight or more, flame retardancy exceeding it is hardly imparted.

Thermoplastic Polymer (D) The thermoplastic polymer (D) which is the base material of the flame-retardant composition of the present invention is a highly crystalline polymer, a low crystalline polymer or a non-crystalline polymer, and It may be any of partially crosslinked polymers, and may be used alone or in combination of two kinds for maintaining. That is, the thermoplastic polymer in the present invention is not limited to any resin, and can be processed by ordinary resin processing means in general, and wax-like and elastomer-like products and thermoplastic resins having both resinous and elastomeric properties. This is a concept that also includes an elastomer.

Therefore, since the melting point (Tm) is not observed and the softening point (Sp) is observed instead of it, even the softening point is unclear like a glassy polymer called a solid solution. Even if it exists, it belongs to the thermoplastic polymer as the base material of the present invention.

Suitable resins and elastomers as the thermoplastic polymer used in the present invention are exemplified below. (1) Polyolefin resin (α-olefin homopolymer or copolymer resin) Polyethylene resin, polypropylene resin, poly-1-butene resin, poly-4-methyl-1-pentene resin, poly-
1-hexene resin, poly-1-octene resin and poly-
1-decene resin. These may be used alone or in combination of two or more as a resin blend.

Among the above polyolefin resins, preferred are crystalline polypropylene resins, for example, crystalline propylene homopolymer resin and propylene as main components,
A crystalline propylene copolymer resin containing ethylene and / or 1-olefin having 4 or more carbon atoms as a copolymer component. In such a crystalline propylene copolymer resin, as the 1-olefin having 4 or more carbon atoms, specifically, 1-pentene, 1-hexene, 4-methyl-1-
Examples thereof include pentene, 1-heptene, 1-octene and 1-decene, and these may be used alone or in combination of two or more as a copolymerization component. The most practical among them is propylene-ethylene crystalline copolymer resin or propylene-1-butene crystalline copolymer resin.

Other preferable ones among the above-mentioned various types are ethylene-based polymers, for example, crystalline ethylene homopolymer or ethylene as a main component, and ethylene and / or 1-olefin having 3 or more carbon atoms as a copolymerization component. And a crystalline ethylene copolymer containing. (2) Polystyrene resin (styrene homopolymer or copolymer) Polystyrene resin (PS), high impact polystyrene resin (HIPS), heat resistant polystyrene resin (styrene-α
-Including methylstyrene copolymer resin), acrylonitrile-styrene copolymer resin (AS), acrylonitrile-butadiene-styrene copolymer resin (ABS) and the like. (3) Acrylic resin (polymer of acrylic acid ester or acrylic acid ester derivative) Polymethyl acrylate resin (PMA), polymethyl methacrylate resin (PMMA) and the like. (4) Polyvinyl resin (polymer of vinyl monomer or its derivative) Polyvinyl chloride resin (PVC), polyvinylidene chloride resin (PVDC) and the like. (5) Polyamide resin (nylon) 6-nylon, 7-nylon, 11-nylon, 12-
Nylon, 6,6-nylon, 6,10-nylon,
6,12-nylon, wholly aromatic nylons such as condensates of terephthalic acid units and p-phenylenediamine units and m-xylylene-adipic acid condensed nylons (MXD
6) and 6- / 6,6-cocondensed nylon and 6- / 1
2-Cocondensed nylon (6) Thermoplastic polyester resin (polymer of aromatic dicarboxylic acid having two carboxyl groups and dihydroxy compound) Polyethylene terephthalate, polybutylene terephthalate and polyphenylene terephthalate (7) Single weight of aromatic compound Copolymers and copolymers Polycarbonate resin (PC), polysulfone resin, polyphenylene ether resin (PPE) and polyurethane resin (PU).

<Elastomers> The thermoplastic polymers constituting the flame-retardant polymer composition of the present invention also include resin blends or "thermoplastic elastomers" containing a small proportion of elastomers. To be done. The "thermoplastic elastomers" include not only simple blends (compositions) of resins and elastomers but also compositions containing elastomers as partially crosslinked products. It is necessary to perform kneading at a temperature higher than the higher temperature among the softening points of the resin type classification and the elastomer components.

Examples of such elastomers include the following. (8) Copolymer elastomer of 1-olefins with each other Ethylene-propylene copolymer elastomer (EP
M), ethylene-propylene-non-conjugated diene copolymer elastomer (EPDM), particularly ethylene-propylene-2-ethylidene-5-norbornene copolymer elastomer (EPDM), propylene-1-butene copolymer elastomer (PBM) ). (9) Conjugated diene homopolymer rubber and copolymer rubber Poly-1,3-butadiene rubber (BR), polyisoprene rubber (IR), acrylonitrile-1,3-butadiene copolymer rubber (NBR), chloroprene Rubber, isobutene-isoprene rubber (IIR: commonly called "butyl rubber"), natural rubber (NR). (10) Condensation polymerization elastomer Polyurethane elastomer, etc.

Conceptual narrowing down of the various elastomers posted above may present the following: Polyolefin-based elastomer Ethylene-propylene copolymer elastomer (EPM) Partially crosslinked product of ethylene-propylene-non-conjugated diene copolymer elastomer composition, propylene crystalline polymer / ethylene-propylene-non-conjugated diene copolymer elastomer composition Partially crosslinked product.

Needless to say, the resins, (co) polymers and elastomers specifically described as the thermoplastic polymer (D) may be used alone or in combination of two or more kinds.

The blending amount of such a thermoplastic polymer (D) is 88.9 to 35% by weight, preferably 8% by weight based on the composition.
It is 1.5 to 54% by weight. <Other additives> In the flame-retardant thermoplastic polymer composition of the present invention, various additives usually added to the thermoplastic polymer, for example, sterically hindered phenolic stabilizers such as antioxidants, A heat resistance stabilizer, an anti-UV agent, an antistatic agent, a copper damage inhibitor, a lubricant, a neutralizing agent, a nucleating agent, a pigment and the like can be appropriately used in combination. Examples of the neutralizing agent include the following.

Complex salts of higher fatty acid metal salts, metal oxides and metal hydroxides such as hydrotalcite or manaceite, talc, mica powder and white carbons. Preparation of Polymer Composition The thermoplastic polymer composition of the present invention can be manufactured, for example, by the following procedure. That is, an oxygen-containing solid compound, a water-insoluble ammonium polyphosphate and a nitrogen-containing organic compound, and other additives, if necessary, are added to a thermoplastic polymer base material in predetermined amounts in suitable agitating and mixing devices such as Henschel mixer (trade name). , A spar mixer or a tumbler mixer, and then mixed by stirring for 1 to 10 minutes. Melt kneading temperature of the obtained mixture is usually 170 to 2 using a roll kneader or a screw extruder, and an extruder with a vent if necessary.
The target flame-retardant composition can be obtained by melting and kneading at 20 ° C. and then extruding the strands into pieces and pelletizing the strands.

[0062]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto. The evaluation methods used in Examples and Comparative Examples are shown below. 1) Flame retardance: UL94V UL Subject 94 (Underland Laboratories, Inc.) "vertical combustion test stipulated in" combustion test of plastic materials for parts of equipment ". Wall thickness of test piece: 1.2 mm (1/12 inch). 2) Flame retardance: Oxygen index (O.I.) Based on Japanese Industrial Standard JIS K7201 (combustion test method for polymer materials according to oxygen index method) 3) Hot water immersion test evaluation test piece (length 100 mm x width 100 mm) × thickness 2mm)
Was molded with an injection molding machine, and the surface electric resistance value of the test piece was measured with a vibration capacitance type microcurrent potentiometer (manufactured by 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. 4) Bleed resistance duration evaluation test piece (length 100 mm x width 100 mm x thickness 2 mm)
Was molded with an injection molding machine, and the surface electric resistance value of the test piece was measured with a vibration capacitance type microcurrent potentiometer (manufactured by Takeda Riken Kogyo Co., Ltd.). Next, the test piece was allowed to stand in a constant temperature and constant humidity chamber adjusted to a temperature of 80 ° C. and a humidity of 80%, and taken out at each elapsed 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 electric resistance value of the test piece was significantly reduced after being taken out from the thermo-hygrostat, it was determined that the bleeding resistance under the high-temperature and high-humidity condition was poor, and the test piece was exposed to the high-temperature and high-humidity condition to obtain the surface electric resistance. The number of days until the resistance value decreased was examined.

The water-insoluble ammonium polyphosphate used in the examples of the present invention was obtained by the following method. Inner volume 5
Melamine-coated ammonium polyphosphate 1000 in a L glass flask (equipped with a heating mixing function and a degassing function)
g and formaldehyde aqueous solution (concentration 37% by weight) 6
4.3 g, water 909 g and methyl alcohol 90.9 g
Was charged and mixed at room temperature. Next, the flask was heated to a temperature of 80 ° C., kept at the same temperature under reflux for 1 hour, and then filtered. The obtained solid was transferred to a drier and dried for 2 hours (100 ° C.) to obtain 1010 g of water-insoluble ammonium polyphosphate.

The melamine-coated ammonium polyphosphate used for obtaining the water-insoluble ammonium polyphosphate was obtained by the following method. 2000 g of ammonium polyphosphate TERRAJU S10 (trademark, manufactured by Chisso Corporation) having an average particle size of 6.4 μm was put into a kneader which had been heated to 280 ° C. in advance, and heated and mixed under a nitrogen gas atmosphere or an inert gas atmosphere for 1 hour. Then ammonia was desorbed. 200 g of melamine is added to ammonia polyphosphate in a state where the amount of ammonia is less than the stoichiometric amount. At this point, close the upper lid of the kneader and in this state 2
Heat and mix at 80 ° C. for 4 hours. The heat mixing was carried out without changing the state of ammonium polyphosphate. In this way, 2100 g 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.

[0066]

Example 1 As a thermoplastic polymer (D), a crystalline propylene-ethylene block copolymer [ethylene content 8.5% by weight, MFR (230 ° C .; 2.16 Kgf) 20 g / 10]
min] (D1) 57.0% by weight and high-density polyethylene [MI (190 ° C; 2.16Kgf) 6.5g / 10min; melting point (Tm) 130 ° C; density 0.952g / cc] (D2)
10% by weight, ethylene-propylene rubber [trade name: EP
-02P (manufactured by Japan Synthetic Rubber Co., Ltd.)] (D3) 10% by weight,
0.5% by weight of magnesium oxide [trade name: Kyowamag (manufactured by Kyowa Chemical Co.)] as the oxygen-containing solid compound (A),
2-Piperazinylene-4 as the nitrogen-containing organic compound (B)
5% by weight of a homopolymer (B1) having morpholino-1,3,5-triazine as a constitutional unit and a water-insoluble ammonium polyphosphate fine powder 17 cross-linked by a reaction with formaldehyde as a water-insoluble ammonium polyphosphate (C) 17 % By weight and 2,6-di-t-as various additives (E)
0.2% by weight of butyl-p-cresol (E1), 0.2% by weight of dimyristyl-β, β'-thiodipropionate (E2) and 0.1% by weight of calcium stearate (E3) were added to a Henschel mixer (trade name). ) And stirred and mixed for 3 minutes. The obtained mixture was melt-kneaded (temperature 200 ° C.) in an extruder (diameter 30 mm) and then extruded to obtain pellets of a flame-retardant polymer composition. Table 1 shows the results obtained by making a predetermined test piece using the obtained pellet and measuring the oxygen index and flame retardancy using the test piece. Table 3 shows the results of hot water immersion test evaluation and bleeding resistance retention days evaluation.

[0067]

Example 2 Pellets prepared according to Example 1 were used except that 1.0% by weight of aluminum oxide was used as the oxygen-containing solid compound (A), and the oxygen index and hardness according to the formulation in Example 1 were measured. The flammability was measured. Table 1 shows the results. Table 3 shows the results of hot water immersion test evaluation and bleeding resistance retention days evaluation.

[0068]

Example 3 2.0% by weight of magnesium hydroxide as the oxygen-containing solid compound (A) and cyanuric sun chloride and ethylenediamine as the nitrogen-containing organic compound (B) at a reaction molar ratio (former / latter = 2/3). Pellets prepared according to Example 1 except that 5% by weight of the product (B2) obtained by the reaction was used were subjected to oxygen index and flame retardancy measurement according to the formulation in Example 1. Table 1 shows the results. Table 3 shows the results of hot water immersion test evaluation and bleeding resistance retention days evaluation.

[0069]

Example 4 1.0 wt% of magnesium oxide as the oxygen-containing solid compound (A) and a reaction molar ratio of cyanuric acid chloride, cyanuric sun chloride and ethylenediamine as the nitrogen-containing organic compound (B) (the former / the latter = 2 / Pellets prepared according to Example 1 except that 5% by weight of the product (B2) obtained by the reaction in 3) was used.
The oxygen index and the flame retardancy were measured in accordance with the prescription in the above. Table 1 shows the results. Table 3 shows the results of hot water immersion test evaluation and bleeding resistance retention days evaluation.

[0070]

Example 5 2.0% by weight of aluminum oxide was used as the oxygen-containing solid compound (A), and the reaction molar ratio of cyanuric acid chloride, cyanuric sun chloride and ethylenediamine was used as the nitrogen-containing organic compound (B) (the former / the latter = 2 / Pellets prepared according to Example 1 except that 5% by weight of the product (B2) obtained by the reaction in 3) was used.
The oxygen index and the flame retardancy were measured in accordance with the prescription in the above. Table 1 shows the results. Table 3 shows the results of hot water immersion test evaluation and bleeding resistance retention days evaluation.

[0071]

[Example 6] Low density polyethylene [MI (190 ° C; 2.16Kgf) 3g / 10min; softening point 96 ° C; density 0.942g / cc; trade name: Petrosene 186 (manufactured by Tosoh Corporation) as a thermoplastic polymer (D) )] (D4) 65.5% by weight, oxygen-containing solid compound (A) as magnesium oxide [trade name: Kyowamag (Kyowa Chemical Co., Ltd.)] 1.0% by weight, as nitrogen-containing organic compound (B) 9% by weight of homopolymer (B1) having 2-piperazinylene-4-morpholino-1,3,5-triazine as a constitutional unit and water-insoluble polyphosphorus crosslinked by reaction with formaldehyde as water-insoluble ammonium polyphosphate (C) 24% by weight of ammonium acid fine powder and 2,6-as various additives (E)
Di-t-butyl-p-cresol (E1) 0.2% by weight, dimyristyl-β, β'-thiodipropionate (E2) 0.2
% By weight and 0.1% by weight of calcium stearate (E3) were charged into a Henschel mixer (trade name) and mixed by stirring for 3 minutes. The obtained mixture was melt-kneaded (temperature 200 ° C.) in an extruder (diameter 30 mm) and then extruded to obtain pellets of a flame-retardant polymer composition. Table 1 shows the results obtained by making a predetermined test piece using the obtained pellet and measuring the oxygen index and flame retardancy using the test piece. Table 3 shows the results of hot water immersion test evaluation and bleeding resistance retention days evaluation.

[0072]

Example 7 Polystyrene resin [MI (190 ° C .; 2.16 Kgf) 1.7 g / 10 min; softening point 97 ° C .; density 1.05 g / cc; trade name: Styron 475S (Asahi Kasei Co.) as a thermoplastic polymer (D) Manufactured)] (D5) 62.5% by weight,
1.0% by weight of magnesium hydroxide [trade name: Kisuma 5A (manufactured by Kyowa Chemical Co., Ltd.)] as the oxygen-containing solid compound (A), and 2-piperazinylene-4-morpholino-1,3 as the nitrogen-containing organic compound (B). 10% by weight of a homopolymer (B1) having 5-triazine as a constitutional unit and 26% by weight of water-insoluble ammonium polyphosphate fine powder crosslinked by the reaction with formaldehyde as the water-insoluble ammonium polyphosphate (C) and various additives ( E) as 2,6-
Di-t-butyl-p-cresol (E1) 0.2% by weight, dimyristyl-β, β'-thiodipropionate (E2) 0.2
% By weight and 0.1% by weight of calcium stearate (E3) were charged into a Henschel mixer (trade name) and mixed by stirring for 3 minutes. The obtained mixture was melt-kneaded (temperature 200 ° C.) in an extruder (diameter 30 mm) and then extruded to obtain pellets of a flame-retardant polymer composition. Table 1 shows the results obtained by making a predetermined test piece using the obtained pellet and measuring the oxygen index and flame retardancy using the test piece. Table 3 shows the results of hot water immersion test evaluation and bleeding resistance retention days evaluation.

[0073]

Comparative Example 1 As a thermoplastic polymer (D), a crystalline propylene-ethylene block copolymer [ethylene content 8.5% by weight, MFR (230 ° C .; 2.16 Kgf) 20 g / 10]
min] (D1) 56.5% by weight and high-density polyethylene [MI (190 ° C; 2.16Kgf) 6.5g / 10min; melting point (Tm) 130 ° C; density 0.952g / cc] (D2)
10% by weight, ethylene-propylene rubber [trade name: EP
-02P (manufactured by Japan Synthetic Rubber Co., Ltd.)] (D3) 10% by weight,
2-Piperazinylene-4 as the nitrogen-containing organic compound (B)
5% by weight of a homopolymer (B1) containing morpholino-1,3,5-triazine as a constituent unit, water-insoluble ammonium polyphosphate (C) as a water-insoluble ammonium polyphosphate fine powder 17 cross-linked by a reaction with formaldehyde % By weight and magnesium sulfate 1.0 which is a solid acid instead of the oxygen-containing solid compound (A) in the examples.
% By weight and 2,6-di-t-butyl-as various additives (E)
0.2% by weight of p-cresol (E1), dimyristyl-β,
0.2% by weight of β'-thiodipropionate (E2) and 0.1% by weight of calcium stearate (E3) were charged into a Henschel mixer (trade name) and mixed with stirring for 3 minutes.
The obtained mixture was melt-kneaded (temperature 200 ° C.) in an extruder (diameter 30 mm) and then extruded to obtain pellets of a flame-retardant polymer composition. Table 2 shows the results obtained by making a predetermined test piece using the obtained pellet and measuring the oxygen index and flame retardancy using the test piece.

[0074]

Comparative Example 2 Pellets prepared according to Example 1 were used according to the formulation of Example 1 except that 1.0% by weight of calcium sulfate, which is a solid acid, was used instead of the oxygen-containing solid compound (A). The oxygen index and flame retardancy were measured. The results are shown in Table 2.

[0075]

Comparative Example 3 As a thermoplastic polymer (D), a crystalline propylene-ethylene block copolymer [ethylene content of 8.5% by weight, MFR (230 ° C .; 2.16 Kgf) 20 g / 10]
min] (D1) 50.5% by weight, magnesium hydroxide as an oxygen-containing solid compound (A) [trade name: Kisuma 5A
(Manufactured by Kyowa Chemical Co., Ltd.)] Pellets prepared according to Example 1 other than 7.0 wt% were subjected to oxygen index and flame retardancy measurement according to the formulation in Example 1. The results are shown in Table 2.

[0076]

[Comparative Example 4] Low-density polyethylene [MI (190 ° C; 2.16Kgf) 3g / 10min; softening point 96 ° C; density 0.942g / cc; trade name: Petrosene 186 (manufactured by Tosoh Corporation) as a thermoplastic polymer (D). )] (D4) 66.5% by weight, 2-piperazinylene-4- as the nitrogen-containing organic compound (B)
9% by weight of a homopolymer (B1) having morpholino-1,3,5-triazine as a constitutional unit and 24% by weight of TERRAJU S10 (manufactured by Chisso Corporation) as powdery ammonium polyphosphate and various additives (E ) As 2,6-di
0.2% by weight of -t-butyl-p-cresol (E1), 0.2% by weight of dimyristyl-β, β'-thiodipropionate (E2) and 0.1% by weight of calcium stearate (E3)
Was charged into a Henschel mixer (trade name) and stirred and mixed for 3 minutes. The obtained mixture was melt-kneaded (temperature 200 ° C.) in an extruder (diameter 30 mm) and then extruded to obtain pellets of a flame-retardant polymer composition. Table 2 shows the results obtained by making a predetermined test piece using the obtained pellet and measuring the oxygen index and flame retardancy using the test piece. Table 3 shows the results of hot water immersion test evaluation and bleeding resistance retention days evaluation.

[0077]

Comparative Example 5 Polystyrene resin [MI (190 ° C .; 2.16 Kgf) 1.7 g / 10 min; softening point 97 ° C .; density 1.05 g / cc; trade name: Styron 475S (Asahi Kasei Co., Ltd.) as a thermoplastic polymer (D) Manufactured)] (D5) 63.5% by weight,
2-Piperazinylene-4 as the nitrogen-containing organic compound (B)
-10% by weight of a homopolymer (B1) having morpholino-1,3,5-triazine as a constitutional unit and 26% by weight of TERRAJU S10 (manufactured by Chisso Corporation) as powdery ammonium polyphosphate and various additives ( E) as 2,
0.2% by weight of 6-di-t-butyl-p-cresol (E1), dimyristyl-β, β′-thiodipropionate (E2)
2% by weight and 0.1% by weight of calcium stearate (E3) were charged into a Henschel mixer (trade name) and mixed by stirring for 3 minutes. The obtained mixture was melt-kneaded (temperature 200 ° C.) in an extruder (diameter 30 mm) and then extruded to obtain pellets of a flame-retardant polymer composition. Table 2 shows the results obtained by making a predetermined test piece using the obtained pellet and measuring the oxygen index and flame retardancy using the test piece. Table 3 shows the results of hot water immersion test evaluation and bleeding resistance retention days evaluation.

[0078]

[Table 1]

[0079]

[Table 2]

[0080]

[Table 3]

[0081]

The flame-retardant thermoplastic polymer composition of the present invention exhibits the following various effects. High flame retardant performance with a low content of flame retardant.

Bleed resistance under high temperature and high humidity conditions (measured by change in resistance value in hot water immersion and continuous days under high temperature and high humidity conditions) is significantly improved. It is possible to provide materials more suitable for the fields of electric appliances, building materials, automobile parts and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication C08K 3/26 KAF 3/32 KAG 3/34 KAH 5/16 KAX 9/04 KCP C08L 21/00 LAY 23/00 KDY 25/04 KFV 61/20 LNG 79/04 LRA 101/00

Claims (13)

[Claims] 1. A flame-retardant thermoplastic polymer composition comprising the following components (A), (B), (C) and (D) in a total amount of 100% by weight: (A) 0.1 to 5% by weight of an oxygen-containing solid compound of an element belonging to Group II, III or IV of the periodic table, (B) 1 to 20% by weight of a nitrogen-containing organic compound, (C) a water-insoluble polyphosphoric acid Ammonium 10-40% by weight, and (D) thermoplastic polymer 88.9-35% by weight. 2. An element belonging to Group II, Group III or Group IV of the periodic table is Ca, Ba, Sr, Mg, Al, Si, Zn, C.
The flame-retardant thermoplastic polymer composition according to claim 1, which is one or more selected from d, Ti, Zr, and Sn. 3. The oxygen-containing solid compound (A) is the compound of the above II to IV.
Hydroxides, basic carbonates, carbonates, carbonate hydrates, silicates, hydrates of silicates, oxides and oxide hydrates of elements belonging to Group II, and 2 belonging to the groups II to IV above 1 selected from complex oxides, complex salts and complex salt hydrates of one or more elements
The flame-retardant thermoplastic polymer composition according to claim 1, which is one or more kinds. 4. The average particle size of the oxygen-containing solid compound (A) is 1
The flame-retardant thermoplastic polymer composition according to any one of claims 1 to 3, which has a thickness of 0 µm or less. 5. Water-insoluble ammonium polyphosphate (C)
Wherein the coating layer comprises ammonium polyphosphate particles and a coating layer for coating the surface of the particles, the coating layer having melamine and a cross-linking compound having a functional group capable of reacting with active hydrogen forming an amino group of the melamine. The flame-retardant thermoplastic polymer composition according to claim 1, which has a crosslinked structure formed by the reaction of. 6. The cross-linking compound has a functional group capable of reacting with active hydrogen belonging to the amino group of melamine, and the functional group is selected from an isocyanate group, a glycidyl group, a carboxyl group, a methylol group and an aldehyde group. The flame-retardant thermoplastic polymer composition according to claim 5. 7. The flame-retardant thermoplastic resin composition according to claim 5, wherein the cross-linking compound is monofunctional or polyfunctional. 8. The coating layer is obtained from melamine-coated ammonium polyphosphate obtained by adding and / or adhering 0.5 to 20% by weight of sublimed melamine to ammonium polyphosphate. Item 5. A flame-retardant thermoplastic resin composition according to item 5. 9. The flame-retardant according to claim 1, wherein the nitrogen-containing organic compound (B) is a homopolymer and / or a copolymer composed of the structural unit represented by the general formula [I]. Thermoplastic Resin Composition: [In formula, X is a formula: -NHR < ¹ >, -NR < ² > R < ³ >, -NHR.
⁴ or -NR ⁵ R ⁶ (wherein R ¹ , R ² and R ³ have 2 carbon atoms
A linear or branched alkyl group having from 6 to 6, R ² and R ³ may be the same or different and may be bonded to each other to form a ring, and R ⁴ , R ⁵ and R ⁶ is carbon number 2
A linear or branched hydroxyalkyl group having 6 to 6 and R ⁵ and R ⁶ may be the same or different,
Z ¹ is a divalent group of piperazine, and is represented by the formula: —HN (C
H ₂ ) mNH- is a divalent group (in the formula, m is 2 to 6).
Or a formula: —NR ⁷ (CH ₂ ) ₁ R ⁸ N— (wherein one or both of R ⁷ and R ⁸ are hydroxyethyl groups, and 1 is a number from 2 to 6). ) Is a group represented by]. 10. The flame-retardant thermoplastic resin composition according to claim 1, wherein the nitrogen-containing organic compound (B) is a reaction product obtained by reacting cyanuric chloride with a diamine. 11. The thermoplastic polymer (D) is an aliphatic thermoplastic resin; an aromatic thermoplastic resin; at least one elastomer selected from an aliphatic elastomer and an aromatic elastomer; The flame-retardant thermoplastic polymer composition according to claim 1, wherein the flame-retardant thermoplastic polymer composition is selected from the group consisting of thermoplastic elastomers comprising one or more thermoplastic resins and one or more elastomers or partially crosslinked elastomers. 12. The thermoplastic polymer according to claim 1, wherein the thermoplastic polymer (D) comprises at least one selected from the following homopolymers and copolymers: (1) Polyolefin (2) Polystyrene resin; (3) Acrylic resin; (4) Polyvinyl resin; (5) Nylon (polyamide resin); (6) Thermoplastic polyester resin; (7) Single weight of aromatic compound Copolymers and copolymers; (8) Thermoplastic 1-olefin copolymer elastomers; (9) Conjugated diene homopolymer rubbers and copolymer rubbers;
And (10) condensation polymerization elastomer. 13. A flame-retardant thermoplastic polymer composition according to claim 12, wherein the thermoplastic polymer comprises at least one selected from the following thermoplastic resins and elastomers: (1) polyethylene resin, polypropylene resin, poly 1
-Butene resin, poly-4-methyl-1-pentene resin,
Poly 1-hexene resin, poly 1-octene resin and poly 1-decene resin; (2) Polystyrene resin (PS), high impact polystyrene resin (HIPS), heat resistant polystyrene resin (styrene-α-methylstyrene copolymer) Resin), acrylonitrile-styrene resin (AS) and acrylonitrile-butadiene-styrene resin (ABS); (3) polymethyl acrylate and polymethyl (meth)
Acrylate; (4) Polyvinyl chloride resin and polyvinylidene chloride resin; (5) 6-nylon, 7-nylon, 11-nylon,
12-nylon, 6,6-nylon, 6,7-nylon, 6,10-nylon, 6,12-nylon, a condensate of a terephthalic acid unit and a p-phenylenediamine unit,
m-xylylene-adipic acid condensed nylon (MXD
6), 6- / 6,6-co-condensed nylon and 6- / 12-
(6) Polyethylene terephthalate, polybutylene terephthalate and polyphenylene terephthalate; (7) Polycarbonate resin (PC), polysulfone resin and polyphenylene ether resin (PPE), and polyurethane resin (PU); (8) Ethylene-propylene copolymer Polymerized elastomer (EP
M), ethylene-propylene-non-conjugated diene copolymer elastomer (EPDM), ethylene-propylene-2-ethylidene-5-norbornene copolymer elastomer (EP
DM) and propylene-1-butene copolymer elastomer (PBM); (9) poly-1,3-butadiene rubber (BR), polyisoprene rubber (IR), acrylonitrile-1.3-butadiene copolymer rubber (NBR). , Chloroprene rubber, isobutene-isoprene rubber (IIR: commonly called "butyl rubber"), natural rubber (NR); and (10) polyurethane elastomer.