JP2001098161A - Flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition having excellent flame retardancy. SOLUTION: This flame retardant resin composition comprises a 1- hydroxyethylidene-1,1'-melamine diphosphonate having <=20 μm mean particle diameter and represented by general formula (1) (M denotes melamine; and n denotes an integer of 1-4). The flame retardant resin composition preferably further contains a hydrated metallic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition containing a low-smoke non-halogen flame-retardant, which can impart excellent flame retardancy to various resins. About things.

[0002]

2. Description of the Related Art Conventionally, halides such as chlorine and bromine, phosphorus compounds, nitrogen compounds, or antimony and boron inorganic compounds have been used as flame retardants for plastics.

[0003] However, in recent years, the level of flame retardancy has become severe in all fields, and high flame retardancy has been demanded. In addition, flame retardants containing bromine and chlorine are dioxins which are toxic to the human body in trace amounts during combustion. It has been pointed out that there is a possibility of occurrence of flammability, and demands for non-halogen flame retardants are increasing.

Examples of the non-halogen flame retardant include a resin composition in which red phosphorus is blended with a curable resin (Japanese Patent Publication No. 59-49942), and hydrated alumina as an epoxy resin flame retardant (Japanese Patent Laid-Open No. No. 25369), surface-treated red phosphorus, hydrated alumina, silica powder (JP-A-58-198521), modified red phosphorus (JP-A-63-156860), and a phenol resin. Calcium oxide and aluminum hydroxide or magnesium hydroxide (JP-A-05-43774), boric acid and antimony trioxide (JP-A-60-81244) for phenolic resin, and intramolecular for polyurethane resin. A compound having three triazine structures (JP-A-53-21241) and the like have been proposed.

On the other hand, for a thermoplastic resin, magnesium hydroxide (Japanese Patent Application Laid-Open No. 54-83) is used for a polyamide resin.
952 and JP-A-54-131645),
And melamine cyanurate (JP-A-53-31759, JP-A-54-91558) and organic sulfonates for polycarbonate (JP-A-50-9853).
No. 9, JP-A-50-98540), sulfide salts (JP-B No. 01-22304), phosphonate compounds and polyphosphates for polyphenylene oxide (JP-A-52-86449), phosphate compounds. Antimony trioxide (JP-A-49-3294)
No. 7) and flame retardants such as polyphosphonates (US Pat. No. 3,719,727) for polyesters have been proposed.

However, among the above flame retardants, red phosphorus is reddish brown, so that the resin is colored by the red phosphorus and coloring is impossible. In addition, the working environment is deteriorated due to the generation of phosphine gas during thermal processing or incineration of the resin, and red phosphorus is coated with a coating agent to suppress this, but the generation of phosphine gas is completely prevented. Cannot be suppressed.

[0007]

SUMMARY OF THE INVENTION Organophosphorus flame retardants have received particular attention as non-halogen flame retardants. The flame-retardant mechanism has a high volatility, and the phosphorus compound vaporized by heating acts as an inhibitor of combustion in the gas phase as a diluent for oxygen gas, a cooling effect for the combustion system due to volatilization, and an effect for suppressing the chemical reaction of combustion. By such means, the combustion of plastic is suppressed. On the other hand, those with low volatility generate thermal decomposition by heating to generate phosphoric acid, which becomes metaphosphoric acid and polymetaphosphoric acid, and forms a non-volatile phosphate polymer on the solid phase or molten layer surface of the plastic to be fired. . Also,
The plastic is carbonized by a dehydration reaction of phosphoric acid to form a carbonized layer, whereby the intrusion of air is blocked, and the supply of heat energy from the outside is blocked to suppress combustion.

At present, various types of organophosphorus flame retardants have been proposed, such as phosphoric acid esters and phosphites. However, most of them have low affinity for resins due to their water solubility and low P content in the compounds. Therefore, in order to enhance the flame-retardant effect, a large amount must be contained in the resin, and the mechanical properties are impaired.

1-Hydroxyethylidene-1,1'-diphosphonic acid and its derivatives are used in various fields as scale inhibitors, anticorrosives, metal surface treating agents, chelating agents, and JP-A-05-86081. Contains 1-
It is disclosed that the 4-melamine salt of hydroxyethylidene-1,1'-diphosphonic acid is an excellent flame retardant compound. However, although the polyphenylene oxide resin (PPO) barely passes the UL94HB level flame retardancy test, it has not yet reached a practical flame retardancy level, and has a flame retardant effect on other resins. Is hardly obtained.

In view of the above problems, the present inventors have conducted intensive studies on non-halogen flame retardants, and as a result, focused on 1-hydroxyethylidene-1,1'-diphosphonic acid having a high P content. 1-hydroxyethylidene which can impart excellent flame retardancy to various resins
An application was made for a flame retardant composition containing a melamine salt of 1,1'-diphosphonic acid (Japanese Patent Application No. 10-251781).

Furthermore, such 1-hydroxyethylidene-
After intensive studies on the melamine salt of 1,1'-diphosphonic acid, the inventors have found that those having a specific range of particle diameters have good dispersibility in resin and further enhance the flame retardant effect, and completed the present invention. I came to. That is, an object of the present invention is to provide a resin composition having excellent flame retardancy.

[0012]

Means for Solving the Problems The flame-retardant resin composition to be provided by the present invention has the following general formula (1) having an average particle diameter of 20 μm or less.

[0013]

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(Wherein, M represents melamine, and n represents 1-4)
Represents an integer. 1) -hydroxyethylidene-1,1'-diphosphonic acid melamine salt represented by the formula (1).

The flame-retardant resin composition comprises 1-hydroxyethylidene-1,1 'represented by the above general formula (1).
-It is preferable to use a melamine diphosphonic acid salt and a hydrated metal compound in combination.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The flame-retardant resin composition of the present invention contains a 1-hydroxyethylidene-1,1′-diphosphonic acid melamine salt represented by the following general formula (1) having an average particle diameter of 20 μm or less as an active ingredient. It is.

[0017]

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In the formula of 1-hydroxyethylidene-1,1'-diphosphonate represented by the general formula (1),
Is 1 to 4, specifically 1-hydroxyethylidene-1,1'-diphosphonic acid.
1 melamine salt 1-hydroxyethylidene-1,1'-diphosphonic acid
2 melamine salt 1-hydroxyethylidene-1,1'-diphosphonic acid
3 melamine salt 1-hydroxyethylidene-1,1'-diphosphonic acid
4 melamine salts.

The above-mentioned 1-hydroxyethylidene-
One or more melamine 1,1'-diphosphonic acid salts are used.

Such 1-hydroxyethylidene-1,
The method for producing the melamine 1'-diphosphonic acid salt is not particularly limited, and a known method can be used. For example, the following general formula (2)

[0021]

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1-hydroxyethylidene-
1,1′-diphosphonic acid and melamine are mixed at 80 ° C. in an aqueous solvent such as water, a mixed solvent of water and acetone, and water and alcohol.
The reaction may be performed at the above temperature.

In the reaction for obtaining the melamine salt of 1-hydroxyethylidene-1,1'-diphosphonic acid as the target product of the above reaction, the starting material, 1-hydroxyethylidene-1,1'-diphosphonic acid represented by the general formula (2), is used. The ratio of the acid to the melamine is usually in the range of 1 to 4 mol of melamine to 1 mol of the phosphonic acid of the general formula (2). What is necessary is just to adjust the usage-amount suitably. After completion of the reaction, the product is filtered and dried, and pulverized until a product having a desired particle size is obtained to obtain a product.

Further, in the present invention, it is an important requirement that the 1-hydroxyethylidene-1,1'-diphosphonic acid melamine salt has an average particle diameter of 20 μm or less. The reason for this is that if the average particle diameter is larger than 20 μm, the dispersibility in the resin becomes worse, and there is a tendency that stable flame retardancy cannot be imparted to the resin molded product,
When the average particle diameter is smaller than 1 μm, it is not practical because of problems such as a pulverizing device.
Those in the range are preferably used.

The average particle size is a value determined by a laser scattering type particle size measuring device (Microtrack).

The above-mentioned 1-hydroxyethylidene-1,
The blending ratio of the 1'-diphosphonic acid melamine salt to various resins is 0.5 as P with respect to 100 parts by weight of the resin.
-30 parts by weight, preferably 1-10 parts by weight. The reason is that if the mixing ratio is less than 0.5 part by weight, it is difficult to obtain a sufficient flame retardant effect, while if it is more than 30 parts by weight, the flame retardant effect becomes large, but the mechanical properties of the molded product deteriorate. It is not preferable because there is a tendency.

The resin that can be used in the present invention is not particularly limited. For example, epoxy resin, phenol resin, polyurethane resin, melamine resin, urea resin, aniline resin, furan resin, alkyd resin, xylene resin, unsaturated resin Curable resin such as polyester resin and diaryl phthalate resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polycarbonate, polyphenylene oxide, polyphenylene ether, nylon 6, nylon 66, nylon 12, polyacetal, polyethylene, polypropylene, polybutadiene, polyacrylonitrile, polystyrene , Polymethyl methacrylate, polyethylene oxide, polytetramethylene oxide, thermoplastic polyurethane, phenoxy resin, polyamide, ethylene On / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene /
Non-conjugated diene copolymer, ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer,
Thermoplastic resins such as ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene / propylene-g-maleic anhydride copolymer, polyester polyether elastomer, polytetrafluoroethylene, and modified products thereof are exemplified. These resins may be homopolymers or copolymers, or may be a mixture of two or more.

Here, the curable resin is a resin having a three-dimensional network structure with an increased molecular weight due to a chemical change caused by the action of heat, a catalyst, ultraviolet rays, or the like. This shows a synthetic resin that becomes semi-permanently insoluble and infusible. In addition, the thermoplastic resin indicates a resin that exhibits fluidity by heating and can be shaped thereby.

In the flame-retardant resin composition of the present invention, the flame-retardant effect can be further enhanced by using it in combination with a hydrated metal compound. The hydrated metal compound, the _{M m O n · XH 2 O} (M with a burn suppressing action by endothermic reaction shown metals, m, n is an integer of 1 or more determined by the valency of the metal, X a is-containing crystal water Or a double salt containing the compound, specifically, calcium hydroxide, magnesium hydroxide, basic magnesium carbonate, calcium hydroxide, barium hydroxide, zirconium hydroxide, dawsonite, stannic acid Zinc, zinc borate, aluminum borate, antimony pentoxide, basic zinc carbonate,
Cobalt oxide, zirconium oxide, tin oxide, aluminum oxide, titanium oxide, magnesium oxide, calcium silicate, borax, zinc molybdate, zinc phosphate, magnesium phosphate, hydrotalcite, hydrocalumite, kaolin, talc, sericite , Pyrophyllite, bentonite, kaolinite, calcium sulfate, zinc sulfate and the like. These hydrated metal compounds may be surface-treated, and the average particle size of these hydrated metal compounds is usually 20 μm or less, preferably 1 to 10 μm.

The mixing ratio of the hydrated metal compound is 100
1 to 200 parts by weight, preferably 1 part by weight,
0 to 100 parts by weight.

Further, in the flame-retardant resin composition of the present invention, a flame-retardant auxiliary can be used in combination. Examples of the flame retardant aid include metal oxides such as antimony trioxide, copper oxide, magnesium oxide, zinc oxide, molybdenum oxide, iron oxide, manganese oxide, aluminum oxide, tin oxide, titanium oxide, nickel oxide, and calcium carbonate. , Carbonates such as barium carbonate, zinc metaborate, metaborates such as barium metaborate, melamine, melamine cyanurate,
Methylolated melamine, (iso) cyanuric acid, melam, melem, melon, succinogamine, melamine sulfate, acetoguanamine sulfate, melam sulfate, guanylmelamine sulfate, melamine resin, BT resin, cyanuric acid,
Isocyanic acid, isocyanuric acid derivatives, melamine isocyanurate, benzoguanamine, melamine derivatives such as acetoguanamine, guanidine compounds, silicone compounds, one or more selected from phosphorus-based flame retardants, and the like. Among them, phosphorus-based flame retardants are particularly preferred.

Examples of the phosphorus-based flame retardant include triethyl phosphate, tricresyl phosphate, triphenyl phosphate,
Cresyl phenyl phosphate, octyl diphenyl phosphate,
Ethyl diethylene phosphate, butyl dihydroxypropylene phosphate, disodium ethylene phosphate, methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid,
Propylphosphonic acid, butylphosphonic acid, 2-methyl-
Propylphosphonic acid, t-butylphosphonic acid, 2,3-
Dimethylbutylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctylphosphinic acid, phenylphosphinic acid, diethylphenylphosphinic acid, diphenylphosphine Acid, bis (4-methoxyphenyl) phosphinic acid, red phosphorus, ammonium phosphate, ammonium polyphosphate, melamine phosphate, guanylurea phosphate, melamine polyphosphate, guanidine phosphate, ethylenediamine phosphate, phosphazene, melamine methylphosphonate One or more selected from salts are mentioned. Among these, red phosphorus, ammonium phosphate, ammonium polyphosphate, melamine phosphate,
Guanylurea phosphate, melamine polyphosphate, and guanidine phosphate are preferably used.

Red phosphorus whose surface is modified by an organic substance and / or an inorganic substance is preferable. For example, phenol resin, epoxy resin, ethylene-vinyl acetate copolymer, melamine-formaldehyde polycondensate, Mg, Ca, Ti , A
Examples thereof include, but are not limited to, hydroxides of l, Co, and Zr and those surface-treated with one or more selected from these oxides.

The mixing ratio of these flame retardant aids is 100
It is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight with respect to parts by weight.

Other components to be added to the resin include phosphorus-based, ionic-based, hindered-phenol-based antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, releasing agents, coloring agents including dyes and pigments. , A cross-linking agent, a softening agent, a dispersant and the like.

If necessary, fibrous and / or granular fillers can be added to significantly improve the rigidity of the resin. As such a filler, for example, glass fiber, carbon fiber, metal fiber, aramid resin,
Asbestos, potassium titanate whisker, walastenite, glass flake, glass beads, talc, mica,
Examples include clay, calcium carbonate, calcium silicate, barium sulfate, titanium oxide, fused silica, crystalline silica, magnesia, and aluminum oxide.

In the present invention, a flame retardant composition comprising a 1-hydroxyethylidene-1,1'-diphosphonic acid melamine salt represented by the general formula (1) and, if necessary, other additives described above. Can be contained in various resins by a generally known method. For example, in the case of a curable resin, a method in which the flame retardant composition of the present invention is mixed with the curable resin and other components at the same time, and the flame retardant composition of the present invention is previously mixed with one of the resin components. , A method of mixing this with a curable resin, if it is a thermoplastic resin, a method of melt-mixing the flame retardant composition of the present invention with an extruder, or after uniformly mechanically mixing particles, and then injecting. Examples include a method of molding at the same time as mixing with a molding machine.

The flame-retardant resin composition of the present invention can be used as a safe plastic material as a semiconductor sealing material, a laminate, a connector, a relay, a switch, a case member, a transformer member, an electric component such as a coil bobbin, a building material, It is sufficiently applicable to fields such as transportation equipment such as automobiles, packaging materials, household daily necessities and the like.

[0039]

The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.

Synthesis Example 1 <Preparation of 1-hydroxyethylidene-1,1'-diphosphonic acid melamine salt> Sample A; 1-hydroxyethylidene-1,1'-diphosphonic acid / 2 melamine salt 18 L (liter) made of stainless steel 15 L of tap water in a container, 1-hydroxyethylidene-
1,3'-diphosphonic acid (hereinafter abbreviated as HEDP) (60% aqueous solution) 1030.0 g (2.99 mo)
l) was added and stirred. After the temperature was raised to 80 ° C., 756.0 g (5.99 mol) of melamine was gradually added and stirred. After completion of the melamine addition, stirring is continued at 80 ° C. until the pH of the reaction solution becomes constant (about 1.3). Thereafter, centrifugal filtration was performed to obtain white crystals. 100 of this crystal
It dried at 24 degreeC for 24 hours, and 1301.5g of target objects were obtained by grind | pulverizing with a mixer. Yield 95.0% (HEDP
Yield).

Next, as a result of measuring C, H and N by elemental analysis, C: 19.9%, H: 4.2%, N: 34.
8%.

Further, the obtained crystals were pulverized with a mixer to prepare 1-hydroxyethylidene-1,1'-diphosphonic acid / 2 melamine salts having various average particle sizes shown in Table 1 below. The average particle size was determined by laser scattering particle size measurement (Microtrack).

Sample B: 1-hydroxyethylidene-
1,1'-diphosphonic acid / 4 melamine salt 18L Stainless steel container 15L tap water, HEDP (60% aqueous solution) 8
33.3 g (2.42 mol) was added and stirred. After the temperature was raised to 80 ° C., 1223.2 g of melamine (9.6 g) was added.
9 mol) was added slowly and stirred. After completion of the melamine addition, the pH of the reaction solution is maintained at 80 until the pH becomes constant (about 5.2).
Stirring was continued at ° C. Thereafter, centrifugal filtration was performed to obtain white crystals. The crystals were dried at 100 ° C. for 24 hours and pulverized with a mixer to obtain 1709.7 g of the desired product. Yield 99.4% (yield based on HEDP).

Next, as a result of measuring C, H and N by elemental analysis, C: 22.5%, H: 4.2%, N: 44.
8%.

The obtained crystals were further pulverized with a mixer to prepare 1-hydroxyethylidene-1,1'-diphosphonic acid / 4 melamine salts having various average particle sizes shown in Table 1 below. The average particle size was determined by laser scattering particle size measurement (Microtrack).

[0046]

[Table 1]

Examples 1 and 2 and Comparative Example 1 Various additives were added to ethyl ethylene acrylate (hereinafter abbreviated as EEA) resin at the compounding ratios shown in Table 2, and the temperature was set at 120 to 130 ° C. Heat roll 5
Kneaded for 10 minutes.

Molding pressure 150 kg /
cm ² , pressurization time 5 minutes, mold temperature 115 ° C, thickness 3
mm sheet, length 125 mm, width 13
mm test pieces were prepared, and the flame retardancy and surface properties of the resin were evaluated. In addition, Kyowa Chemical Co., Ltd. product (Kisuma 5A) was used for magnesium hydroxide.

<Flame Retardancy Test> The flame retardancy test is a vertical combustion test (94) of a material obtained by classifying a resin processed into a length of 125 mm × a width of 13 mm × a thickness of 3 mm adjusted as described above into UL94.
V-0, 94V-1 and 94V-2). Table 4 shows the results. Table 3 shows the UL 94 availability conditions.

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

[Table 4]

(Note 1) The surface properties were evaluated by touch. (Note 2) The after-flame time after flame contact in Table 4 corresponds to Test 2 in Table 3. The second after-flame time is flame contact test using the same test piece as the first test. It is the after-flame time.

From the results in Table 4, it can be seen that, by reducing the particle size of the melamine phosphonate, the dispersibility in the resin is improved, and in the flame-retardant test based on UL94, there is no variation in data and the resin is stable. It can be seen that improved flame retardancy can be imparted.

Examples 3 to 4 and Comparative Example 2 Various additives were blended in a blending ratio shown in Table 5 with novolak resin prepared at a molar ratio of formaldehyde / phenol = 0.9. The mixture was kneaded with a hot roll set at 90 ° C. for 5 minutes. After the pulverization, a molded product having a predetermined shape was prepared using a universal press at a molding pressure of 250 kg / cm ² , a pressing time of 60 seconds, and a mold temperature of 150 ° C.

The flame retardancy test was evaluated by the same operation method as in Examples 1 and 2. Table 6 shows the results.

[0057]

[Table 5]

[0058]

[Table 6]

Examples 5 to 12 and Comparative Examples 3 to 6 Various additives shown in Table 7 were added to various resins, and 30 m
ASTM D-6 by injection molding using a mΦ screw extruder
A tensile test specimen specified in No. 38 was prepared, and strength and elongation were measured based on the test method of JIS K7113.

Similarly, a test piece for evaluating flame retardancy based on UL94 was prepared, and the flammability was evaluated. Table 8 shows the results. The conditions of melt extrusion, pellet drying, and injection molding for each resin are shown below.

Polybutylene terephthalate (hereinafter referred to as P
Extrusion; 250-290 ° C / 150 rpm drying; 110 ° C / 12 hours molding; 250-290 ° C / die 80 ° C ・ Nylon 6 extrusion; 250-300 ° C / 150 rpm drying; 100 ° C / 24 hours molding 250-300 ° C / die 80 ° C ・ Polycarbonate extrusion; 260-320 ° C / 75 rpm drying; 120 ° C / 12 hours molding; 260-320 ° C / die 110 ° C ・ A mixture of polyphenylene oxide and polystyrene (mixing weight ratio; 60:40; hereinafter abbreviated as PPO) Extrusion; 240-310 ° C / 70 rpm Drying; 110 ° C / 4 hours Molding; 240-320 ° C / die 90 ° C

[0062]

[Table 7]

[0063]

[Table 8]

Examples 13 to 15 and Comparative Examples 7 to 8 A polypropylene resin (hereinafter abbreviated as PP) was added to Table 9
Various additives were added at the mixing ratio shown in
The mixture was kneaded for 5 minutes with a hot roll set for 5 minutes. Melt extrusion was performed at a screw rotation speed of 87 rpm. A test piece based on UL94 was prepared by injection molding (cylinder temperature: 230 ° C., mold temperature: 50 ° C.), and the flammability was evaluated. Table 9 shows the results. Note that red phosphorus whose surface was modified with aluminum hydroxide and titanium hydroxide was used.

[0065]

[Table 9]

[0066]

As described above, the flame-retardant resin composition of the present invention uses a non-halogen flame retardant having excellent resin dispersibility. It has the effect of imparting flammability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C08K 5/3477 C08K 5/3477 5/5317 5/5317 C09K 21/04 C09K 21/04 21/12 21 / 12 (72) Inventor Nobuo Matsumoto 9-11-1, Kameido, Koto-ku, Tokyo F-term within Nippon Kagaku Kogyo Co., Ltd. CC031 CC121 CC161 CC181 CC182 CD001 CF001 CG001 CH021 CH061 CK021 CL001 CM011 DA058 DE048 DE077 DE087 DE097 DE187 DE238 DE267 DE287 DG047 DG057 DH047 DH048 DH058 DJ007 FB007 FD028 FE018 138 GF00 GG02 GJ02 GL00 GN00 GQ00

Claims (5)

[Claims] 1. The following general formula (1) having an average particle size of 20 μm or less. (Wherein, M represents melamine and n represents an integer of 1 to 4) 1-hydroxyethylidene-1,1 ′
-A flame-retardant resin composition containing a melamine diphosphonic acid salt. 2. The flame-retardant resin composition according to claim 1, comprising the melamine salt of 1-hydroxyethylidene-1,1'-diphosphonic acid according to claim 1 and a hydrated metal compound. 3. The flame retardant resin composition according to claim 2, further comprising a flame retardant auxiliary. 4. The flame-retardant resin composition according to claim 3, wherein the flame-retardant auxiliary is a phosphorus-based flame retardant. 5. The phosphorus-based flame retardant is at least one selected from red phosphorus, ammonium phosphate, ammonium polyphosphate, melamine phosphate, guanylurea phosphate, melamine polyphosphate and guanidine phosphate. 4
The flame-retardant resin composition according to the above.