JPH1046034A - Flame-retardant resin composition and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition capable of imparting high flame retardance to a thermoplastic resin by using a non-halogen-based flame retardant and having good moldability and mechanical properties and obtain a molding by molding the resin composition. SOLUTION: This resin composition is obtained by blending 100 pts.wt. thermoplastic resin with 0.1-100 pts.wt. red phosphorus and 0.5-100 pts.wt. salt of triazine-based compound with cyanuric acid or isocyanuric acid. Number- average dispersed particle diameter of red phosphorus in the resin composition is 50-0.01μm and number-average dispersed particle diameter of the salt of the triazine-based compound with a cyanuric acid or isocyanuric acid is 100-0.01μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant resin composition and a molded article using a non-halogen flame retardant.
More specifically, electrical and electronic devices such as connectors, relays, switches, case members, transformer members, coil bobbins, etc., have excellent flame retardancy in high-grade thin-walled parts, do not deteriorate mechanical properties, and have excellent electrical characteristics. The present invention relates to a flame-retardant resin composition and molded article suitable for parts, automobile parts, and machine parts.

[0002]

2. Description of the Related Art Polyester resins represented by polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexane dimethylene terephthalate, and the like, and thermoplastic resins such as polycarbonate resins, polyamide resins, and polyphenylene oxide resins have been known for their excellent properties. Taking advantage of its characteristics, it is being used as an injection molding material in a wide range of fields such as mechanical parts, electric parts, and automobile parts. On the other hand, since these thermoplastic resins are inherently flammable, in order to be used as industrial materials, in addition to the general balance of chemical and physical properties, fire safety, that is, flame retardancy is required. Often.

As a method of imparting flame retardancy to a thermoplastic resin, a method of compounding a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant auxiliary into the resin is generally used. However, this method has problems such as a large amount of smoke generated during combustion.

Accordingly, in recent years, it has been strongly desired to use a flame retardant containing no halogen in order to overcome the disadvantages of these halogen-based flame retardants.

Heretofore, as a method of making a thermoplastic resin flame-retardant without using a halogen-based flame retardant, it has been widely known to add a hydrated metal compound such as aluminum hydroxide or magnesium hydroxide. In order to obtain sufficient flame retardancy, it is necessary to add a large amount of the above-mentioned hydrated metal compound, which has a disadvantage that the inherent properties of the resin are lost.

On the other hand, as a method of making a thermoplastic resin flame-retardant without using such a hydrated metal compound, adding red phosphorus is disclosed in JP-A-5-78560 and JP-A-5-28771.
No. 19, JP-A-5-295164, JP-A-5-339
No. 417, and the like. However, any resin composition is a useful flame-retardant resin material that does not use a halogen-based flame retardant, but the advanced flame-retardant effect is insufficient or the excellent mechanical properties of the thermoplastic resin are impaired. Or the flame retardant resin composition has a problem that the amount of decomposition gas when the resin is heated and retained is large.

[0007]

SUMMARY OF THE INVENTION The present invention uses a non-halogen flame retardant to impart high flame retardancy to a thermoplastic resin, has good moldability, and has good mechanical properties. It is an object to obtain a flame-retardant resin composition.

[0008]

Means for Solving the Problems In view of the above circumstances, the present inventors have conducted intensive studies and as a result, have found that a thermoplastic resin contains red phosphorus and cyanuric acid or isocyanuric acid together with a compound represented by the above formula (1). Together with a salt with
It has been found that when these are finely dispersed, the performance balance is specifically excellent, and the present invention has been achieved.

That is, the present invention relates to (A) a thermoplastic resin 1
A resin composition comprising (B) 0.1 to 100 parts by weight of red phosphorus and (C) 0.5 to 100 parts by weight of a salt comprising a triazine compound and cyanuric acid or isocyanuric acid with respect to 00 parts by weight. The number average dispersed particle diameter of red phosphorus in the resin composition is 50 to 0.01 μm, and the number average dispersed particle diameter of a salt composed of a triazine compound and cyanuric acid or isocyanuric acid is 100 to 0. 0.11 μm, the flame-retardant resin composition wherein the triazine-based compound is a compound represented by the general formula (1),

Embedded image (However, in the above formula, R ¹ , R ² , R ³ , and R ⁴ are the same or different and are hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, or —CONH ₂ . -NR ¹ R ² or -NR ³ R ⁴ the same group or those with independently hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, -NH ₂ group or selected from -CONH _2,, The flame-retardant resin composition further comprises 5 to 140 parts by weight of a filler based on the flame-retardant resin composition. 0.11 to 10 parts by weight, a flame retardant resin composition wherein the triazine compound is melamine, and a flame retardant wherein the thermoplastic resin (A) is a thermoplastic polyester resin. Resin composition and filler The flame-retardant resin composition as glass fiber, the flame-retardant resin composition further containing 0.01 to 3 parts by weight of a hindered phenol-based stabilizer with respect to the flame-retardant resin composition, A molded article obtained by molding a flammable resin composition, and a molded article in which the molded article is used for a mechanical mechanism part, an electric part, an electronic part, or an automobile part.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant resin composition of the present invention will be specifically described below.

The thermoplastic resin (A) of the present invention is a synthetic resin which exhibits fluidity when heated, and can be molded by utilizing this. Specific examples thereof include thermoplastic polyesters such as polyester, non-liquid crystalline polyester and liquid crystalline polyester, polycarbonate, polyamide, polyphenylene oxide, phenoxy resin, polyolefin-based polymers such as polyphenylene sulfide, polypropylene and polyethylene, and ethylene / propylene copolymers. Polymer, ethylene / 1-butene copolymer, ethylene /
Propylene / non-conjugated diene copolymer, ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer and ethylene / propylene-g-maleic anhydride copolymer Coalesce, polyolefin copolymers such as ABS resin, polyester polyether elastomer,
Polyesters Elastomers such as polyester elastomers, and mixtures of two or more of these synthetic resins are mentioned, and non-liquid crystalline polyesters are particularly preferably used. Specific examples of the non-liquid crystalline polyester resin include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycyclohexane dimethylene terephthalate, and polyethylene-1,2-bis (phenoxy) ethane-4. And 4'-dicarboxylate, and copolymerized polyesters such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / decanedicarboxylate and polycyclohexane dimethylene terephthalate / isophthalate. , Among these, mechanical properties, polybutylene terephthalate with good balance of moldability,
Polybutylene naphthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate and polyethylene terephthalate can be preferably used, and particularly, polybutylene terephthalate can be preferably used.

The red phosphorus (B) used in the present invention can be blended with a thermoplastic resin without any treatment, but the red phosphorus ignites during storage or gradually dissolves in water. Since it has the property of dissolving, a material subjected to a treatment for preventing this is preferably used. Examples of such a method for treating red phosphorus include a method in which a small amount of aluminum hydroxide or magnesium hydroxide is added to red phosphorus to catalytically suppress the oxidation of red phosphorus, or a method in which red phosphorus is coated with paraffin or wax to remove red water. Method of suppressing contact with, stable method by mixing with ε-caprolactam and trioxane, stable by coating red phosphorus with thermosetting resin such as phenolic, melamine, epoxy and unsaturated polyester To convert red phosphorus to copper, nickel, silver,
A method of treating with an aqueous solution of a metal salt such as iron, aluminum, and titanium to precipitate and stabilize a metal phosphorus compound on the surface of red phosphorus; aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide for red phosphorus And the like, a method of stabilizing the surface of red phosphorus by electroless plating with iron, cobalt, nickel, manganese, tin, etc., and a method of combining these methods. To stabilize by coating with a thermosetting resin such as phenolic, melamine, epoxy, or unsaturated polyester, or to coat red phosphorus with aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide, etc. And more preferably, red phosphorus is converted to aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide, etc. Phenolic onto the coating, melamine, epoxy, a method for stabilizing by coating doubly thermosetting resin such as unsaturated polyester. The average particle size of red phosphorus before being blended with the resin is defined as the number average dispersed particle size of red phosphorus in the obtained resin composition, flame retardancy, mechanical strength, surface properties, and electrical properties of molded articles. From the viewpoint of (tracking resistance), the thickness is preferably 50 to 0.01 μm, and more preferably 45 to 0.1 μm.

The number average dispersed particle diameter of red phosphorus in the flame-retardant resin composition of the present invention is determined by the flame retardancy, mechanical strength, surface properties and electrical properties (tracking resistance) of the obtained molded article. Is from 50 to 0.01 μm, preferably from 30 to
It is 0.05 μm, more preferably 20 to 0.1 μm.

The amount of red phosphorus (B) in the present invention is 0.1 to 100 parts by weight, preferably 0.5 to 80 parts by weight, more preferably 1 to 100 parts by weight of the thermoplastic resin.
５０50 parts by weight.

The salt of cyanuric acid or isocyanuric acid (C) used in the present invention is an adduct of cyanuric acid or isocyanuric acid with a triazine compound, usually in a ratio of 1: 1 (molar ratio), In some cases, it is an adduct having a composition of 1: 2 (molar ratio). Of the triazine compounds, those that do not form a salt with cyanuric acid or isocyanuric acid are excluded.

Examples of the triazine-based compound include compounds represented by the following general formula (1).

[0017]

Embedded image (However, in the above formula, R ¹ , R ² , R ³ , and R ⁴ are the same or different and are hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, or —CONH ₂ . -NR ¹ R ² or -NR ³ R ⁴ the same group or those with independently hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, -NH ₂ group or selected from -CONH _2,, In the general formula (1), R ¹ , R ² , R ³ , and R ⁴ are the same or different, hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, or —CONH 2. Here, the aryl group has 6 to 15 carbon atoms,
It is preferable that the alkyl group has 1 to 10 carbon atoms, the aralkyl group has 7 to 16 carbon atoms, and the cycloalkyl group has 4 to 15 carbon atoms. R is the same group as -NR1 R2 or -NR3 R4 in the above formula, or independently of these, hydrogen, aryl group, alkyl group, aralkyl group, cycloalkyl group, -NH2, or -C
An aryl group having 6 to 15 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and an aralkyl group having 7 to 16 carbon atoms.
And cycloalkyl groups having 4 to 15 carbon atoms are preferred.

Specific examples of R ¹ , R ² , R ³ and R ⁴ include hydrogen, phenyl, p-toluyl, α-naphthyl, β-naphthyl, methyl, ethyl and n-propyl. Group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, hydroxymethyl group, methoxymethyl group, benzyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 2-methyl-1-pentyl group, Examples thereof include a 4-methyl-1-cyclohexyl group and an amide group, and among them, hydrogen, a phenyl group, a methyl group, a hydroxymethyl group, a methoxymethyl group, a benzyl group, and an amide group are preferable.

Specific examples of R include an amino group,
Amide group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, mono (hydroxymethyl) amino group, di (hydroxymethyl) amino group, mono (methoxymethyl) amino group, di (methoxymethyl) amino group, Phenylamino group, diphenylamino group, hydrogen, phenyl group, p-toluyl group, α-naphthyl group, β
-Naphthyl group, methyl group, ethyl group, n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
tert-butyl group, benzyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 2-methyl-1-
Examples thereof include a pentyl group and a 4-methyl-1-cyclohexyl group, among which hydrogen, an amino group, an amide group, a methyl group, a mono (hydroxymethyl) amino group, a di (hydroxymethyl) amino group, and a mono (methoxymethyl) group An amino group, a di (methoxymethyl) amino group, a phenyl group, and a benzyl group are preferred.

Of the salts of the compound represented by the general formula (1) with cyanuric acid or isocyanuric acid, melamine, benzoguanamine, acetoguanamine,
Amide-4,6-diamino-1,3,5-triazine,
Mono (hydroxymethyl) melamine, di (hydroxymethyl) melamine and tri (hydroxymethyl) melamine salts are preferred, especially melamine, benzoguanamine,
Acetoguanamine salts are preferred.

The salt of the triazine compound and cyanuric acid or isocyanuric acid is prepared by mixing a mixture of the triazine compound and cyanuric acid or isocyanuric acid with a water slurry and mixing them well to form fine particles of both salts. After that, this slurry is a powder obtained by filtering and drying, and is different from a mere mixture. The salt does not need to be completely pure, and a somewhat unreacted triazine-based compound or cyanuric acid or isocyanuric acid may remain. In addition, the average particle size of the salt before being mixed with the resin is determined by the number average dispersed particle size of the salt in the obtained resin composition, the flame retardancy, mechanical strength, surface properties and electrical properties (mold resistance) of the molded product. It is preferably from 100 to 0.01 μm, more preferably from 80 to 10 μm, from the viewpoint of tracking performance). If the salt has poor dispersibility, a dispersant such as tris (β-hydroxyethyl) isocyanurate may be used in combination.

The number average dispersed particle size of the salt of a triazine compound and cyanuric acid or isocyanuric acid in the flame-retardant resin composition of the present invention is determined by the flame retardancy of the obtained molded article,
From the viewpoint of mechanical strength, surface properties and electrical properties (tracking resistance), it is 100 to 0.01 μm, preferably 90 to 0.1 μm, more preferably 80 to 0.5 μm.
m.

The amount of the salt used is the thermoplastic resin (A) 10
0.5 to 100 parts by weight, preferably 2 to 0 parts by weight
The amount is from 80 to 80 parts by weight, more preferably from 3 to 70 parts by weight.

When the flame-retardant resin composition of the present invention is further added with a fluorine-based resin, the drop (drip) of droplets during combustion is suppressed. Examples of such fluororesins include polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, and (tetrafluoroethylene / Ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / ethylene) copolymer and the like. Among them, polytetrafluoroethylene, (tetrafluoroethylene / (Perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer, and polyvinylidene fluoride are preferred. Polytetrafluoroethylene, (tetrafluoroethylene / ethylene) copolymer are preferable.

The amount of the fluorine-based resin is usually 0.0 to 100 parts by weight of the thermoplastic resin in view of mechanical properties and moldability.
1 to 10 parts by weight, preferably 0.1 to 5 parts by weight,
More preferably, it is 0.2 to 3 parts by weight.

It has been found that when the flame retardant resin composition of the present invention is further used in combination with a hindered phenol-based stabilizer, extremely good hydrolysis resistance is maintained even when exposed to high temperatures for a long period of time. As such a stabilizer, for example, triethylene glycol-bis [3- (3-t-butyl-
5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 2,2-thio-diethylenebis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-t-butyl-4-hydroxybenzyl) benzene, bis or tris (3-t-butyl-6-methyl-4-hydroxyphenyl) propane, N, N'-hexamethylenebis (3,5-di- t-butyl-4-hydroxy-hydrocinnamamide), N, N'-trimethylenebis (3,5-
Di-t-butyl-4-hydroxy-hydrocinnamide) and the like.

In the present invention, such a hindered phenol-based stabilizer can be added as needed, and the amount of the hindered phenol-based stabilizer added at that time is usually the thermoplastic resin (A). 0.0 to 100 parts by weight
1 to 3 parts by weight, preferably 0.01 to 3 parts by weight, more preferably 0.03 to 0.5 parts by weight.

By adding a fibrous and / or granular filler to the flame-retardant resin composition of the present invention, the strength, rigidity, heat resistance and the like can be greatly improved.

Specific examples of such fillers include glass fiber, carbon fiber, metal fiber, aramid fiber, asbestos, potassium titanate whisker, wollastenite, glass flake, glass beads, talc, mica, clay,
Examples thereof include calcium carbonate, barium sulfate, titanium oxide, and aluminum oxide. Among them, chopped strand type glass fibers are preferably used.

The amount of these additives is determined by the amount of the thermoplastic resin (A) 10
The amount is preferably from 5 to 140 parts by weight, particularly preferably from 5 to 100 parts by weight, based on 0 parts by weight.

The flame retardant resin composition of the present invention can be improved in stability, strength, heat resistance and the like during extrusion and molding by further adding a stabilizer for red phosphorus.

Specific examples of such a stabilizer for red phosphorus include cadmium oxide, zinc oxide, copper oxide, iron oxide, cobalt oxide, manganese oxide, molybdenum oxide, titanium oxide, and tin oxide. Cadmium oxide and titanium oxide are preferably used.

[0033] The amount of these additives is the thermoplastic resin (A) 10
The amount is preferably 0.01 to 5 parts by weight, particularly preferably 0.1 to 3 parts by weight, per 0 parts by weight.

Further, as far as the object of the present invention is not impaired, the flame-retardant resin composition of the present invention is not limited to hindered phenols, such as phosphorus-based or sulfur-based antioxidants, heat stabilizers, and ultraviolet absorbers. One or more ordinary additives such as a lubricant, a releasing agent, and a coloring agent including a dye or a pigment can be added.

The flame-retardant resin composition of the present invention is usually produced by a known method. For example, a thermoplastic resin (A), red phosphorus (B), a salt of cyanuric acid or isocyanuric acid (C), and other necessary additives may be supplied to an extruder or the like with or without premixing. It is prepared by melt-kneading. In this case, for example, a single-screw extruder equipped with a "Unimelt" type screw, a twin-screw extruder, a kneader of a kneader type and the like can be used,
In particular, since the aspect ratio is controlled, it is preferable to use a screw by inserting or not inserting several kneading elements into the screw.

The flame-retardant resin composition thus obtained can be molded by a generally known method, and can be molded articles such as injection molding, extrusion molding and compression molding, and molded articles such as sheets and films. Among them, it is particularly suitable for use in injection molded articles, and can be usefully used as mechanical mechanism parts, electric / electronic parts, and automobile parts by utilizing its features.

[0037]

The effects of the present invention will be described in more detail with reference to the following examples. Here, all parts are parts by weight. The measuring method of each characteristic is as follows.

(1) Mechanical Properties ASTM was applied to dumbbell test pieces obtained by injection molding.
The tensile yield strength and elongation at break were measured according to D-638.

(2) Flame Retardancy Flame retardancy of a test piece for flame retardancy evaluation obtained by injection molding and press molding was evaluated in accordance with the evaluation standard defined in UL94. The flame retardancy level is V-0>V-1>V-2> H
It decreases in the order of B.

(3) Number Average Dispersion Particle Size A thin piece was cut out from the test piece for evaluating flame retardancy using an ultramicrotome and photographed using an optical microscope (transmitted light) and a transmission electron microscope. The average value of the maximum diameter of 100 individuals randomly selected from the micrograph was determined, and this value was defined as the number average dispersed particle size.

(4) Tracking Resistance A 80 mm × 80 mm, 3 mm thick test piece obtained by injection molding was subjected to a tracking resistance test in accordance with the IEC112 test standard, and a CTI (Comparative T) was tested.
(Tracking Index) was measured. Obtained C
From TI (V), CTI >> 600 rank 0, 400 <<
CTI <600 rank 1, 250 << CTI <400 rank 2, 170 << CTI <250 rank 3,100
<< CTI <170 is classified as rank 4, and 0 << CTI <100 is classified as rank 5.

Reference Example 1 A commercially available reagent, red phosphorus (Wako Pure Chemical Industries, Ltd.) was classified to have a particle size of 32 μm.
The following powder was obtained. This powder is referred to as red phosphorus A. Similarly, a powder having a particle size of 50 μm or more is classified as red phosphorus B. Also,
The surface-treated red phosphorus (Nova Red 120, manufactured by Rin Kagaku Kogyo Co., Ltd.) was classified into powder having a particle size of 32 μm or less.
This powder is referred to as red phosphorus C.

Reference Example 2 An equimolar mixture of melamine and cyanuric acid was prepared in a weight ratio of 10%.
After suspending in hot water twice and stirring well, the slurry was filtered to obtain a white cake. Then this cake is 70
The powder was vacuum-dried at ℃ and crushed to classify into powder having a particle size of 50 μm or less. The powder thus obtained is referred to as cyanuric acid salt A. Similarly, the powder having a particle size of 100 μm or more is pulverized into cyanuric acid salt B.

Reference Example 3 A powder having a particle size of 50 μm or less is referred to as cyanurate C, and a powder having a particle size of 100 μm or more is referred to as cyanurate D in the same manner as in Reference Example 2 except that benzoguanamine is used instead of melamine.

Examples 1-22, Comparative Examples 1-20 Tables 1-4 correspond to 100 parts by weight of polybutylene terephthalate (hereinafter abbreviated as PBT) having an intrinsic viscosity of 0.85 (25 ° C., o-chlorophenol solution). Various types of red phosphorus,
Mix a salt of cyanuric acid or isocyanuric acid and other additives, screw diameter 30 mm, L / D45.
5 twin-screw extruder (TEX-3, manufactured by Nippon Steel Corporation)
0: The screw uses two screws of 3.5 mm that engage with each other with two threads, and screw elements consisting of 10 kneading disks inclined at 45 degrees with L / D = 4 are provided in reverse order. , And a single screw extruder with a screw diameter of 30 mm and L / D22 (VS30-22, full flight screw, manufactured by Tanabe Plastics Co., Ltd.)
And melt extruded at a resin temperature of 260 ° C. After drying the obtained pellets, A was obtained by injection molding (mold temperature 80 ° C.).
Tensile test piece and U specified in STMD-638
A test piece for evaluating flame retardancy based on L94 was prepared.

The measurement results of the number average dispersed particle size, flame retardancy, and mechanical properties of each sample are summarized in Tables 1 and 2.

The stabilizers in the table are pentaerythryl-tetrakis [3- (3,5-di-tert-butyl-4-).
Hydroxyphenyl) propionate] (“IR-1010” manufactured by Ciba-Geigy). GF represents glass fiber.

[0048]

[Table 1] From Examples 1 to 6, it is possible to finely disperse PBT with finely divided red phosphorus and cyanuric acid salt of the present invention by using a screw-shaped twin-screw extruder having a strong kneading force. As a result, it can be seen that high flame retardancy can be imparted and excellent mechanical properties are exhibited.

Further, if both the finely divided red phosphorus and cyanuric acid salt are blended from Example 7, it can be finely dispersed in the resin even by a single screw extruder having a low kneading force. However, as compared with Examples 1 to 6, the dispersed particle size in the resin was slightly larger.
/ 32 "flame retardancy.

From Comparative Examples 1 to 3, PBT containing no red phosphorus or cyanurate has excellent mechanical properties, but is inferior in flame retardancy. From Comparative Example 4, only the classified and finely divided red phosphorus is blended. Even if a screw-shaped twin-screw extruder with a strong kneading force is used, the particle diameter of red phosphorus in the resin composition becomes large due to secondary agglomeration, a high degree of flame retardancy is not exhibited, and mechanical properties are deteriorated. It turns out that it is big. Further, from Comparative Example 5, even if a twin-screw extruder in which only the classified and refined cyanuric acid salt was blended into a screw shape having a strong kneading force was used, the particle diameter of the cyanuric acid acid salt in the resin composition was secondary. Larger due to aggregation,
It can be seen that a high degree of flame retardancy is not exhibited, and that the mechanical properties are greatly reduced.

Comparative Examples 6 to 9 show that even if red phosphorus and cyanuric acid salt are used in combination with PBT, excellent flame retardancy cannot be obtained if the number average dispersed particle size in the resin composition is large, and the tensile properties deteriorate. Is large.

In the present invention, excellent tracking resistance can be exhibited by blending both red phosphorus and cyanuric acid salt. However, resins without GF are inherently excellent in tracking resistance (60
0 V or higher, which is equal to or higher than the measurement limit), and it was not possible to obtain a difference in tracking resistance from Examples 1 to 7 and Comparative Examples 1 to 9 as measured values.

[0053]

[Table 2] In Examples 8 to 14 and Comparative Examples 10 to 19, GF was blended. According to Examples 8 to 14 and Comparative Examples 10 to 19, even when reinforced with glass fiber, both the classified and refined red phosphorus and cyanurate were blended to form a screw having a high kneading force in a twin-screw extrusion. It can be seen that, by performing the process, fine dispersion can be achieved in the resin, high flame retardancy can be imparted, and further excellent mechanical properties are exhibited.

On the other hand, from Comparative Examples 10 to 12, it can be seen that PBT reinforced with glass fibers containing no red phosphorus or cyanurate has excellent mechanical properties but poor flame retardancy.

Also, from Comparative Example 13, even if a screw-shaped twin-screw extruder containing only classified and finely divided red phosphorus and having a strong kneading force was used, the particle size of the red phosphorus in the resin composition was still small. It can be seen that the particle size increases due to the secondary aggregation, the flame retardancy does not appear, and the mechanical characteristics are greatly reduced.

Further, from Comparative Example 14, the particle size of the cyanurate in the resin composition was also measured using a twin-screw extruder in which only the classified and refined cyanurate was compounded and the screw was shaped into a strong kneading force. Is increased by secondary aggregation, high degree of flame retardancy is not exhibited, and mechanical property is greatly reduced.

From Comparative Examples 10 to 12, the tracking resistance of PBT containing glass fibers was ranked 2 (390).
V), while using a twin-screw extruder in which both red phosphorus and cyanurate finely divided by the classification of Examples 8 to 14 were blended and the kneading force was used to form a screw, It can be seen that tracking resistance is improved to rank 1 (430 to 450 V) by finely dispersing.

From Comparative Examples 15 to 19, even when red phosphorus and cyanuric acid salt were blended, it was found that the effect of improving tracking resistance was small when the dispersed particle size in the resin composition was large.

[0059]

[Table 3] According to Examples 15 to 19 and Comparative Examples 20 to 22, when both red phosphorus and cyanurate are mixed with PBT, even if the particle size of red phosphorus and cyanurate is large at the time of mixing, a screw having a strong kneading power is obtained. By using a twin-screw extruder having a shape, the number average dispersed particle diameter of red phosphorus and cyanuric acid in the resin composition can be reduced, and high flame retardancy and excellent tensile properties are exhibited. I understand. Further, if the number average dispersed particle size of either red phosphorus or cyanuric acid in the resin composition is large, excellent flame retardancy cannot be obtained, and the tensile properties are greatly reduced.

[0060]

[Table 4] The same can be said for the case where the glass fibers of Examples 20 to 24 and Comparative Examples 23 to 25 are reinforced.

From the above, it can be seen that high flame retardancy is provided only by reducing the number average dispersed particle diameter of both red phosphorus and cyanuric acid salt in the resin composition, and excellent mechanical properties are exhibited. Recognize. In addition, P reinforced with glass fiber
In BT, it turns out that tracking resistance improves.

Examples 25 to 31, Comparative Examples 26 to 35 Commercially available poly (1,4-cyclohexanedimethylene terephthalate) (PCT), bisphenol A type polycarbonate (PC), nylon 6 (PA6), nylon 66
(PA66), 100 parts by weight of ABS resin, and red phosphorus, cyanuric acid or isocyanuric acid salt and other additives shown in Tables 5 to 8 were mixed with 100 parts by weight of the ABS resin.
Melt extrusion was performed using a screw extruder and a single screw extruder. After drying the obtained pellet, ASTM D-6 by injection molding.
A test piece for flame retardancy evaluation based on UL94 was prepared by a tensile test piece specified in No. 38 and a press molding.

The measurement results of the number average dispersed particle size, flame retardancy, and mechanical properties of each sample are summarized in Tables 5 to 8.

[0064]

[Table 5]

[Table 6]

[Table 7]

[Table 8] From Examples 25 and 26 and Comparative Examples 26 to 29, excellent flame retardancy cannot be obtained only by blending only red phosphorus or only a triazine compound into the PCT resin. Also, even if red phosphorus and cyanurate are used in combination with the PCT resin, if the number average dispersed particle size in the resin composition is large, excellent flame retardancy cannot be obtained and the tensile properties are reduced. It can be seen that a high flame retardancy is imparted by reducing both the number average dispersed particle diameters of the cyanuric acid salt and excellent mechanical properties are exhibited.

From Examples 27 and 28 and Comparative Examples 30 and 31, even if red phosphorus and cyanurate were used in combination with PC resin, if the number average dispersed particle size was large, excellent flame retardancy could not be obtained, and tensile properties were not obtained. It can be seen that, by reducing the number average particle diameter of both red phosphorus and cyanurate, high flame retardancy is imparted and excellent mechanical properties are exhibited.

According to Examples 29 and 20 and Comparative Examples 32-34, excellent flame retardancy cannot be obtained only by blending red phosphorus alone in a nylon resin. Also, even if red phosphorus and cyanurate are used in combination, if the number average dispersed particle size is large, excellent flame retardancy cannot be obtained and the tensile properties deteriorate, but the number average of both red phosphorus and cyanurate is reduced. It can be seen that a high degree of flame retardancy is provided by reducing the dispersed particle size, and excellent mechanical properties are exhibited.

From Example 31 and Comparative Example 35, even when red phosphorus and cyanuric acid salt were used in combination with the ABS resin, if the number average dispersed particle size was large, excellent flame retardancy was not obtained, and the tensile properties were deteriorated. However, by reducing the number average dispersed particle size of both red phosphorus and cyanurate, high flame retardancy is imparted,
It can be seen that excellent mechanical properties are exhibited.

As described above, in many thermoplastic resins, a high degree of flame retardancy is imparted by reducing the number average dispersed particle diameter of both red phosphorus and cyanuric acid salt, and excellent mechanical properties are exhibited. Can be.

[0069]

【The invention's effect】

(1) The flame-retardant resin composition of the present invention containing red phosphorus having a specific number average dispersed particle size and a salt of cyanuric acid and a melamine compound having a specific number average dispersed particle size is known in the art. It shows a higher flame retardant effect than other red phosphorus-containing flame retardant resin compositions.

(2) The flame-retardant resin composition obtained by the present invention is not only excellent in flame retardancy but also an excellent flame-retardant formulation which does not adversely affect the properties of the thermoplastic resin. It has excellent surface appearance and electrical properties (tracking resistance), and is useful as mechanical parts, electrical parts, and automobile parts.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication C08L 27:12)

Claims (10)

[Claims] (A) 100 to 100 parts by weight of a thermoplastic resin, (B) 0.1 to 100 parts by weight of red phosphorus, and (C) a salt of 0.5 to 500 parts by weight of a triazine compound and cyanuric acid or isocyanuric acid. A resin composition containing 100 parts by weight, wherein the number average dispersed particle diameter of red phosphorus in the resin composition is 5%.
A flame-retardant resin composition having a number average dispersion particle diameter of from 0 to 0.01 μm and a number average dispersion particle diameter of a salt comprising a triazine compound and cyanuric acid or isocyanuric acid of 100 to 0.01 μm. 2. The flame-retardant resin composition according to claim 1, wherein the triazine compound is a compound represented by the general formula (1). Embedded image (However, in the above formula, R ¹ , R ² , R ³ , and R ⁴ are the same or different and are hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, or —CONH ₂ . -NR ¹ R ² or -NR ³ R ⁴ the same group or those with independently hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, -NH ₂ group or selected from -CONH _2,, Is.) 3. The composition according to claim 1, further comprising 5 to 140 parts by weight of a filler based on 100 parts by weight of the thermoplastic resin (A).
The flame-retardant resin composition according to the above. 4. The flame-retardant resin composition according to claim 1, further comprising 0.01 to 10 parts by weight of a fluororesin based on 100 parts by weight of the thermoplastic resin (A). 5. The flame-retardant resin composition according to claim 1, wherein the triazine compound is melamine. 6. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin (A) is a thermoplastic polyester resin. 7. The flame-retardant resin composition according to claim 3, wherein the filler is glass fiber. 8. The flame-retardant resin composition according to claim 1, further comprising 0.01 to 3 parts by weight of a hindered phenol-based stabilizer based on 100 parts by weight of the thermoplastic resin (A). 9. A molded article obtained by molding the flame-retardant resin composition according to claim 1. 10. The molded article according to claim 9, wherein the molded article is for mechanical mechanism parts, electric parts, electronic parts or automobile parts.