JP3484803B2 - Flame retardant resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition containing a non-halogen flame retardant. More specifically, it has excellent mechanical properties, does not deteriorate hydrolysis resistance, and is suitable for electrical / electronic equipment parts such as connectors, relays, switches, case members, transformer members, coil bobbins, automobile parts, and mechanical parts. Resin composition.

[0002]

2. Description of the Related Art Polyester resins represented by polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexane dimethylene terephthalate, etc., or thermoplastic resins such as polycarbonate resin, polyamide resin, polyphenylene oxide resin, etc. Taking advantage of the characteristics, it is being used as an injection molding material in a wide range of fields such as machine mechanism parts, electric parts, and automobile parts. On the other hand, these thermoplastic resins are inherently flammable, and therefore, in order to use them as industrial materials, in addition to the balance of general chemical and physical properties, safety against flames, that is, flame retardancy is required. In many cases.

A common method for imparting flame retardancy to a thermoplastic resin is to compound a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant aid into the resin. However, this method has a problem that a large amount of smoke is generated during combustion.

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

Up to now, copolymerization and blending of phosphorus compounds have been widely known as a method of flame-retarding a thermoplastic resin without using a halogen-based flame retardant, and various methods have been proposed mainly for fiber applications. ing. For example, as a typical method for making a thermoplastic polyester resin flame-retardant, a phosphonic acid unit or a phosphinic acid unit is copolymerized with polyester (Japanese Patent Application Laid-Open Nos. 51-54691 and 50-69).
56488), copolymerization of a monomer having a cyclic phosphinite skeleton as a pendant (JP-A-52-9808).
9, JP-A-55-5916, JP-A-60-
240755, etc.), blends of polyphosphonates (US Pat. No. 3,719,727), blends of red phosphorus (JP-A-49-74240), and the like. Of these, JP-A-55-5916 and JP-A-49-7
Although there is an example of a composition for injection molding in Japanese Patent No. 4240, the conventional flame-retardant technology using phosphorus compounds is basically intended for fiber and film applications, and is not intended for resin molded products.

Further, a technique of adding an aromatic phosphate or an aromatic phosphate oligomer to make it flame-retardant is disclosed in Japanese Patent Laid-Open Publication No.
Although disclosed in, for example, Japanese Patent Application Laid-Open No. 8-90348 and Japanese Patent Application Laid-Open No. 48-91147, these also mainly aim at making the fibers flame-retardant. On the other hand, European Published Patent EP491
No. 986 discloses a method of adding a resorcin type aromatic phosphate oligomer to the flame retardant PBT alloy molded article.
Further, Japanese Patent Laid-Open No. 05-70671 discloses a method of adding resorcin type aromatic bisphosphate, melamine cyanurate and an inorganic filler to polyalkylene terephthalate.

[0007]

A thermoplastic resin composition for injection molding has a heat resistance for maintaining the mechanical performance of the molded product and the reliability of the molded product even when used under high temperature and high humidity. And hydrolysis resistance is required. In this respect, it has been found that the conventional technique has the following problems.

(1) In copolymerization of a phosphonic acid unit or a phosphinic acid unit, the P (= O) -O bond of the main chain is easily hydrolyzed, and as a result, the hydrolysis resistance of the molded product is significantly deteriorated.

(2) When a monomer containing phosphorus is copolymerized, particularly when polyester is used to obtain flame retardancy at a level required for electric / electronic parts, a large amount of copolymerization occurs, and the melting point of the resin itself, The crystallization rate is significantly reduced, and its use as an injection molding resin is extremely limited.

(3) In the blend of red phosphorus, there are problems such as deterioration of mechanical properties of the thermoplastic resin and coloring.
The flame retardant effect on the thermoplastic resin is small.

(4) In a blend of resorcin-type aromatic phosphate or resorcin-type aromatic phosphate oligomer, these phosphates are easily hydrolyzed,
The hydrolysis product acts catalytically on the hydrolysis reaction of the resin itself, so that durability performance is deteriorated. Further, when a resin composition containing a resorcin-type aromatic phosphate or a resorcin-type aromatic phosphate oligomer is formed into a molded article, a bleed phenomenon in which these compounds seep out to the surface of the molded article is observed.

[0012] As described above, there are many problems in applying the conventional technique mainly for fibers and films to molding applications. Further, the flame-retardant technique using resorcin-type aromatic phosphate or resorcin-type aromatic phosphate oligomer developed for molded articles also has the above problems.

That is, the present invention uses a non-halogen flame retardant, imparts a high degree of flame retardancy to a thermoplastic resin, and at the same time has good moldability and good hydrolysis resistance and mechanical properties. An object is to obtain a flame-retardant resin composition.

[0014]

The inventors of the present invention have made extensive studies in view of the above circumstances and, as a result, have found that in molding applications, aromatic phosphates or phosphate oligomers having a specific structure, and cyanuric acid or isocyanuric acid and The present inventors have found that the combined use of the compound represented by the formula (2) and a salt has a particularly excellent performance balance, and arrived at the present invention.

That is, the present invention provides (A) a thermoplastic polyester, a phenoxy resin, and a poly
Phenylene oxide resin, polyphenylene sulfide resin
An aromatic phosphate and / or an aromatic phosphate oligomer having a structure represented by (B) the general formula (1) per 100 parts by weight of the thermoplastic resin which is a mixture of one or more kinds selected from fats . A flame-retardant resin composition comprising 5 to 100 parts by weight and (C) 0.5 to 100 parts by weight of a salt represented by the general formula (2) and cyanuric acid or isocyanuric acid. Is.

[0016]

[Chemical 4] (However, in the above formula, R ¹ , R ² , R ³ , and R ⁴ represent the same or different hydrogen atoms or an alkyl group having 1 to 5 carbon atoms. Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are the same. Or a different phenyl group or a phenyl group substituted with a halogen-free organic residue, and X is a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , C
Represents HPh, and Ph represents a phenyl group. n represents the number average degree of polymerization, and a value at which the number average molecular weight is 500 ≦ n
It takes a range of <40. Further, k and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less. )

[Chemical 5] (However, in the above formula, R ⁵ , R ⁶ , R ⁷ , and R ⁸ are the same or different hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, or —CONH ₂ .
R is the same group as —NR ⁵ R ⁶ or —NR ⁷ R ⁸ in the above formula, or independently of these, hydrogen, aryl group, alkyl group, aralkyl group, cycloalkyl group, —N
It is a group selected from H ₂ or —CONH ₂ . ) The thermoplastic resin (A) referred to here is a thermoplastic polyester , a phenoxy resin, a polyphenylene oxide resin,
It is a mixture of one or more selected from polyphenylene sulfide resins. Further, specific examples of the thermoplastic polyester resin include polyethylene terephthalate,
Polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycyclohexane dimethylene terephthalate and polyethylene-1,2-bis (phenoxy) ethane-4,4'-dicarboxylate, as well as polyethylene isophthalate / Copolyesters such as terephthalate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / decane dicarboxylate and polycyclohexane dimethylene terephthalate / isophthalate can be mentioned. Among them, well-balanced mechanical properties and moldability can be mentioned. Polybutylene terephthalate, polybutylene naphthalate, polycyclohexane dimethylene terephthalate, polyethylene naphthalate Fine polyethylene terephthalate is particularly preferably used. Further, one or two selected from thermoplastic polyester and phenoxy resin, polyphenylene oxide resin, polyphenylene sulfide resin.
As a compounding ratio of the mixture with at least one kind, 5 to 200 parts by weight of another resin is preferable to 100 parts by weight of the thermoplastic polyester.

The aromatic phosphate or aromatic phosphate oligomer (B) used in the present invention is a compound having a repeating unit represented by the above formula (1),
The number average degree of polymerization n is not less than a value at which the number average molecular weight is 500 and less than 40 (value at which the number average molecular weight is 500 ≦
n <40), but preferably 2 or more and less than 40, particularly preferably 3 or more and less than 40. The number average molecular weight is not particularly limited as long as it is 500 or more, but it is preferably 550 to 25,000, particularly preferably 700 to
It is 20,000. If the number average molecular weight is less than 500, it will be volatilized during melt-kneading and may bleed out on the surface of the molded product, so it cannot be used. The number average molecular weight and the number average degree of polymerization are GPC (Gel Permeati
on Chromatography, converted to polystyrene).

In the above formula (1), k and m are 0 respectively.
It is an integer of 2 or more and 1 + m is an integer of 0 or more and 2 or less, preferably k and m are integers of 0 or more and 1 or less, particularly preferably k and m are 1 respectively.

In the above formula (1), R ¹ , R ² , R ³ ,
R ⁴ represents the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms. Here, specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
ert-butyl group, n-pentyl group, 2-pentyl group,
Examples include 3-pentyl group and neopentyl group,
Hydrogen, a methyl group and an ell group are preferable, and hydrogen is particularly preferable.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different phenyl groups or phenyl groups substituted with halogen-free organic residues. Specific examples thereof include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a naphthyl group, an indenyl group, and an anthryl group, but a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a naphthyl group are preferable, Particularly, a phenyl group, a tolyl group and a xylyl group are preferable.

X is a direct bond, O, S, SO ₂ , C
(CH ₃ ) ₂ , CH ₂ , and CHPh are represented, and Ph represents a phenyl group.

The aromatic phosphate or aromatic phosphate oligomer is generally produced according to the following chemical reaction formula (4). In this case, a low molecular weight phosphate such as triaryl phosphate may be mixed as a by-product. In that case, there is no particular problem as long as the number average molecular weight of the entire phosphate mixture is not less than 500.

[0023]

[Chemical 6] Specific examples of the aromatic phosphate and / or aromatic phosphate oligomer (B) in the present invention include the following examples, but the invention is not limited thereto.

[0024]

[Chemical 7]

[Chemical 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13] Of these aromatic phosphates or aromatic phosphate oligomers, Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are
It is preferable that the same or different phenyl, tolyl, or xylyl groups, and k and m each be 1. In particular, the bisphenol A type aromatic phosphate or the bisphenol A type aromatic phosphate oligomer represented by the following formula (3) is flame retardant. It is preferably used from the viewpoints of properties, mechanical properties, and economic efficiency.

[0025]

[Chemical 14] The amount of the aromatic phosphate and / or aromatic phosphate oligomer (B) added in the present invention is 0.5 to 100 parts by weight, preferably 1 to 80 parts by weight, more preferably 5 parts by weight with respect to 100 parts by weight of the thermoplastic resin. ˜50 parts by weight. If the addition amount is less than 0.5 parts by weight, the flame retardant effect is not sufficient, and if it exceeds 100 parts by weight, the mechanical properties of the molded product deteriorate, which is not preferable.

The flame retardancy of the resin composition is determined by the phosphorus content in the composition. Therefore, in the case of an aromatic phosphate and / or aromatic phosphate oligomer having a high phosphorus content, a sufficiently high flame retardancy can be achieved with a small amount of the compound, but an aromatic phosphate and / or an aromatic phosphate having a low phosphorus content can be achieved. In the case of an oligomer, a large amount of compound is required. The phosphorus content required for flame retardancy of the thermoplastic resin composition (phosphorus content in the composition) is usually 0.1 to 10%, preferably 0.2 to 8%, particularly preferably 0.5 to 5%. Is.

The salt (C) of cyanuric acid or isocyanuric acid used in the present invention is an adduct of cyanuric acid or isocyanuric acid and the compound represented by the general formula (2), and usually 1 It is an adduct having a composition of 1: 1 (molar ratio), and optionally 1: 2 (molar ratio). Of the compounds represented by the general formula (2), those which do not form a salt with cyanuric acid or isocyanuric acid are excluded.

In the general formula (2), R ⁵ , R ⁶ and R
⁷ , R ⁸ are the same or different hydrogen, aryl group, alkyl group, aralkyl group, cycloalkyl group, or -C
OH ₂ . Here, the aryl group has 6 to 1 carbon atoms.
5, an alkyl group having 1 to 10 carbon atoms,
The aralkyl group is preferably one having 7 to 16 carbon atoms and the cycloalkyl group is preferably one having 4 to 15 carbon atoms. R is the same group as -NR ⁵ R ⁶ or -NR ⁷ R ⁸ in the above formula, or independently of these, hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, -NH ₂ ,
Or a group selected from -CONH ₂ , wherein the aryl group has 6 to 15 carbon atoms, the alkyl group has 1 to 10 carbon atoms, and the aralkyl group has 7 to 16 carbon atoms, Cycloalkyl group has 4 carbon atoms
Those of -15 are preferable.

Specific examples of R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen, phenyl group, p-toluyl group, α-naphthyl group, β-naphthyl group, methyl group, ethyl group and n-propyl group. 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 4-methyl-1-cyclohexyl group and amide group, and among them, hydrogen, phenyl group, methyl group, hydroxymethyl group, methoxymethyl group, benzyl group and amide group are preferable.

A specific example of R is an amino group,
Amido 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
ert-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 them, hydrogen, amino group, amido group, methyl group, mono (hydroxymethyl) amino group, di (hydroxymethyl) amino group, mono (methoxymethyl). Amino group, di (methoxymethyl) amino group, phenyl group and benzyl group are preferred.

Of the salts of the compound represented by the general formula (2) with cyanuric acid or isocyanuric acid, melamine, benzoguanamine, acetoguanamine, 2-
Amido-4,6-diamino-1,3,5-triazine,
Salts of mono (hydroxymethyl) melamine, di (hydroxymethyl) melamine and tri (hydroxymethyl) melamine are preferred, especially melamine, benzoguanamine,
The salt of acetoguanamine is preferred.

The salt of the compound represented by the general formula (2) with cyanuric acid or isocyanuric acid is prepared by forming a mixture of the compound represented by the general formula (2) with cyanuric acid or isocyanuric acid into an aqueous slurry. It is a powder obtained by mixing and forming both salts into fine particles, and filtering and drying this slurry, which is different from a simple mixture. This salt does not need to be completely pure, and may be a slightly unreacted compound of formula (2) or cyanuric acid,
Isocyanuric acid may remain. The form of this salt is not particularly limited, but it is preferable to use the one obtained as a powder as fine as possible from the viewpoint of mechanical strength and surface property of the molded article obtained from the composition of the present invention. It is particularly preferable that the average particle size before blending with the resin is 100 μm or less. When the salt has poor dispersibility, a dispersant such as tris (β-hydroxyethyl) isocyanurate may be used in combination.

The amount of the above salt used is the amount of the thermoplastic resin (A) 10
0.5 to 100 parts by weight, preferably 2 to 0 parts by weight
˜80 parts by weight, more preferably 3 to 70 parts by weight. If the amount of the salt used is less than 0.5 parts by weight, the flame retardancy-improving effect is not recognized, and if it exceeds 100 parts by weight, the mechanical properties and surface appearance of the molded product are impaired, which is not preferable.

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

From the viewpoint of mechanical properties and moldability, the amount of fluorine resin added is usually 0.0 with respect to 100 parts by weight of the thermoplastic resin.
1 to 10 parts by weight, preferably 0.1 to 5 parts by weight,
It is more preferably 0.2 to 3 parts by weight.

The addition of the fluororesin is particularly effective when a mixture of polyester and one or more selected from a phenoxy resin, a polyphenylene oxide resin and a polyphenylene sulfide resin is used as the thermoplastic resin.

The aromatic phosphate or aromatic phosphate oligomer used in the present invention has an extremely slight action of promoting the hydrolysis of the thermoplastic resin having a dehydration condensation structure such as an ester bond as compared with other conventionally known phosphorus flame retardants. However, it has been found that when a hindered phenol-based stabilizer is further used in combination, extremely good hydrolysis resistance is maintained even when exposed to high temperature for a long time. Examples of such stabilizers include triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] and 1,6-hexanediol-bis [3- (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-hydrocinnamide), 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 if necessary, and the amount of the hindered phenol-based stabilizer added at that time is usually the thermoplastic resin (A). 0.0 for 100 parts by weight
It is 1 to 3 parts by weight, preferably 0.01 to 1 part by weight, and more preferably 0.03 to 0.5 part by weight.

Further, with respect to the flame-retardant resin composition of the present invention, an antioxidant such as a phosphorus-based or sulfur-based antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, and a mold release agent within a range not impairing the object of the present invention. , And one or more usual additives such as colorants including dyes and pigments can be added.

Although not particularly essential, by adding a fibrous and / or granular filler to the flame-retardant resin composition of the present invention, strength, rigidity, heat resistance, etc. can be significantly increased. Can be improved.

Specific examples of such fillers include glass fiber, carbon fiber, metal fiber, aramid fiber, asbestos, potassium titanate whiskers, wallastonite, glass flakes, glass beads, talc, mica, clay,
Examples thereof include calcium carbonate, barium sulfate, titanium oxide and aluminum oxide, and among them, chopped strand type glass fiber is preferably used.

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

The flame-retardant resin composition of the present invention is usually produced by a known method. For example, a method of melt-mixing a thermoplastic resin (A), an aromatic phosphate and / or an aromatic phosphate oligomer (B), a salt of cyanuric acid or isocyanuric acid (C) and other necessary additives in an extruder, Alternatively, there may be mentioned a method in which particles are mechanically mixed uniformly and then the particles are simultaneously molded by an injection molding machine.

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 products, and by utilizing its characteristics, it can be usefully used as machine parts and automobile parts.

[0045]

EXAMPLES 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 Dumbbell test pieces obtained by injection molding
Tensile yield strength and breaking elongation were measured according to D-638.

(2) LOI (Limited Oxygen Concentration Index) A 150 mm × 6 mm × 1 mm strip-shaped test piece was prepared from the pellet, and the LOI was measured according to ASTM D-2863. The larger the LOI, the higher the flame retardancy.

(3) A 127 mm × 12.7 mm × 0.8 mm strip-shaped test piece was prepared from the flame-retardant pellet, and the flame-retardant property was evaluated according to the evaluation standard defined in UL94.

The flame retardancy level is V-0>V-1>V-2>
It decreases in the order of HB.

(4) Hydrolysis-resistant dumbbell test pieces were treated in a thermo-hygrostat at 80 ° C. and 95% RH for a predetermined time, and the change in molecular weight before and after treatment was measured by GP.
It was measured by C (polystyrene conversion value), and the rate of change was used as a measure of hydrolysis resistance.

(5) Crystallization characteristics Only polyester pellets were measured by DSC. Both the temperature increase and the temperature decrease were performed at a rate of 20 ° C./minute, and after the temperature increase, the maximum temperature was kept at 260 ° C. for 10 minutes and then the temperature was decreased. Tm represents the melting point, and Tc represents the crystallization temperature from the molten state.

The abbreviations and structures of the aromatic phosphate compounds used in the examples and comparative examples are shown below.

[0053]

[Chemical 15]

[Chemical 16] The number average molecular weight of the above compound was as follows.

A: 580 (n = 0.56) B: 710
(N = 0.86) C: 620 (n = 0.72) D:
830 (n = 1.06) E: 800 (n = 1.06)
F: 1590 (n = 1.00) G: 580 (n =
1.02) H: 600 (n = 1.05) I: 790
(N = 1.38) The above number average molecular weight is a value measured using GPC under the following conditions.

Apparatus: Waters, Column: TSK-G
2500H / TSK-G4000H Solvent: NMP (0.02N lithium chloride), Flow rate:
0.5mL / min Detection: UV (260nm)

When the salts of cyanuric acid used in this example were observed with an electron microscope, the average particle size (average value of the number of solids 100) was smaller than 100 μm in all cases. The ratio Comparative Examples 1-18 intrinsic viscosity of 0.85 (25 ° C., o-chlorophenol solution) (hereinafter abbreviated as PBT) polybutylene terephthalate various phosphorous compounds shown in Table 1 relative to 100 parts by weight cyanuric acid or The isocyanuric acid salt and other additives were mixed and melt-extruded at a resin temperature of 260 ° C. using a 30 mmΦ twin-screw extruder. The obtained pellets are dried and then subjected to ASTMD by injection molding (mold temperature 80 ° C).
The tensile test piece specified by -638 was produced. In addition, press molding was performed to prepare LOI measurement samples and UL94-based flame retardancy evaluation samples.

[0057] Each sample of LOI, flame retardancy, mechanical properties, color tone of the molded article are shown summarizes <br/> in Table 2 the measurement results of hydrolysis resistance.

Regarding the blending amounts of the aromatic phosphate compound and various phosphorus flame retardants, the weight% of phosphorus in the composition is also described in addition to the number of parts.

The antioxidant in the table means pentaerythrutyl-tetrakis [3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionate] (“IR-1010” manufactured by Ciba-Geigy). GF represents glass fiber.

[0060]

[0061]

[Table 1]

[0062]

[0063]

[Table 2]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

Examples 1 to 14 Phenoxy resin (bisphenol A and epichlorohydrin) having a polystyrene-reduced weight average molecular weight of 59000 measured by GPC with respect to polybutylene terephthalate having an intrinsic viscosity of 0.85 (25 ° C., o-chlorophenol solution). In the table of condensates with and, expressed as phenoxy), the polystyrene reduced weight average molecular weight measured by GPC is 120,000.
Poly (2,6-dimethyl-1,4-phenylene) oxide (hereinafter abbreviated as PPO) having a melt viscosity of 800 poise (3
Table 3 shows linear type polyphenylene sulfides (hereinafter abbreviated as PPS) at 20 ° C. and a shear rate of 1000 / sec, phosphorus compounds such as aromatic phosphate compounds, salts of cyanuric acid or isocyanuric acid, and other additives. They were mixed in a ratio and melt-extruded using a 30 mmΦ twin-screw extruder. The pellets obtained are injection molded by ASTM
A tensile test piece specified in D-638 was produced. In addition, press molding was performed to prepare LOI measurement samples and UL94-based flame retardancy evaluation samples.

Table 4 shows the measurement results of LOI, flame retardancy, mechanical properties, color tone of molded products, hydrolysis resistance and the like of each sample.

Regarding the blending amounts of the aromatic phosphate compound and various phosphorus flame retardants, the weight% of phosphorus in the composition is also described in addition to the number of parts.

[0080]

[Table 3]

[0081]

[Table 4]

[0082] From the evaluation results based on LOI values and UL94 embodiment 1,3,5,7,9,11,13, and a polyester resin, a phenoxy resin, PPO, aromatic of the present invention to a mixture of PPS It can be seen that excellent flame retardancy can be imparted by adding a phosphate and a cyanuric acid salt. Moreover, Examples 2, 4, 6, 8, 10, 1
The same can be said from Nos . 1, 12 , and 14 when reinforced with glass fiber .

Examples 15 to 28 The same resin compositions as in Examples 1 to 14 were prepared except that 0.3 part by weight of Polyflon MPA FA-100 (polytetrafluoroethylene powder) manufactured by Daikin Industries, Ltd. was further added. Table 5 shows the measurement results of LOI, flame retardancy, mechanical properties, color tone of molded products, hydrolysis resistance, etc. of each sample.

[0084]

[Table 5]

The compositions of Examples 15 to 28 were all V-
It showed 0 level flame retardancy, and no drop of liquid droplets (drip) was observed during the combustion test. Also, mechanical properties,
The color tone and hydrolysis resistance of the molded product were at the same level as in Examples 1-14 .

[0086]

【The invention's effect】

(1) The combined use of the aromatic phosphate and the salt of cyanuric acid or isocyanuric acid used in the present invention exhibits a higher flame retarding effect than other conventionally known phosphorus-based flame retardants. It is also an excellent flame-retardant formulation that has good hydrolysis resistance and does not adversely affect the properties of the thermoplastic resin.

(2) The flame-retardant resin composition obtained by the present invention has not only good flame retardancy but also excellent mechanical properties, melt flowability and surface appearance, and deterioration in hydrolysis resistance. Since it is not present, it is useful as mechanical parts, electric parts, and automobile parts.

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI C08L 67/02 C08L 67/02 71/10 71/10 71/12 71/12 81/02 81/02 101/00 101/00 (56) References JP-A-6-157880 (JP, A) JP-A-6-80885 (JP, A) JP-A-7-233311 (JP, A) JP-A7-166073 (JP, A) Kaihei 7-157595 (JP, A) JP 7-276465 (JP, A) JP 54-112958 (JP, A) JP 3-281652 (JP, A) JP 53-45355 ( (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08

Claims (9)

(57) [Claims] 1. A thermoplastic polyester (A) and a phenoki
Si resin, polyphenylene oxide resin, polyphenylene
Mixture with one or more selected from sulfide resins
0.5 to 100 parts by weight of (B) an aromatic phosphate and / or an aromatic phosphate oligomer having a structure represented by the general formula (1), and (C) a general formula, relative to 100 parts by weight of a compounded thermoplastic resin. A flame-retardant resin composition comprising a compound represented by (2) and 0.5 to 100 parts by weight of a salt of cyanuric acid or isocyanuric acid. [Chemical 1] (However, in the above formula, R ¹ , R ² , R ³ , and R ⁴ represent the same or different hydrogen atoms or an alkyl group having 1 to 5 carbon atoms. Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are the same. Or a different phenyl group or a phenyl group substituted with a halogen-free organic residue, and X is a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , C
Represents HPh, and Ph represents a phenyl group. n represents the number average degree of polymerization, and a value at which the number average molecular weight is 500 ≦ n
It takes a range of <40. Further, k and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less. ) [Chemical 2] (However, in the above formula, R ⁵ , R ⁶ , R ⁷ , and R ⁸ are the same or different hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, or —CONH ₂ .
R is the same group as —NR ⁵ R ⁶ or —NR ⁷ R ⁸ in the above formula, or independently of these, hydrogen, aryl group, alkyl group, aralkyl group, cycloalkyl group, —N
It is a group selected from H ₂ or —CONH ₂ . ) 2. The flame-retardant resin composition according to claim 1, wherein k and m are each 1 in the formula of the aromatic phosphate and / or aromatic phosphate oligomer (B) represented by the general formula (1). . 3. An aromatic phosphate and / or an aromatic phosphate oligomer (B) represented by the general formula (1).
The flame-retardant polymer composition according to claim 1, wherein Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are the same or different phenyl, tolyl, or xylyl groups. 4. The flame-retardant resin composition according to claim 1, wherein the aromatic phosphate and / or aromatic phosphate oligomer (B) represented by the general formula (1) is represented by the following formula (3). [Chemical 3] 5. The flame-retardant resin composition according to claim 1, wherein the salt (C) consisting of the compound represented by the general formula (2) and cyanuric acid or isocyanuric acid has an average particle size of 100 μm or less. 6. The flame-retardant resin composition according to claim 1, wherein the compound represented by the general formula (2) is melamine. 7. 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). 8. The flame-retardant resin composition according to claim 1, which further comprises 0.01 to 3 parts by weight of a hindered phenolic stabilizer based on 100 parts by weight of the thermoplastic resin (A). 9. The thermoplastic resin (A) of 100 parts by weight is further mixed with 5 to 140 parts by weight of a filler.
The flame-retardant resin composition described.