JPH07216235A - Flame retardant resin composition - Google Patents

Abstract

PURPOSE:To obtain a flame retardant resin composition containing a specific phosphonitrile liner polymer, etc., a specific salt and a specific thermoplastic resin at a specific ratio, excellent in mechanical characteristics and resistance to hydrolysis and useful for electric and electronic parts, etc. CONSTITUTION:This flame-retardant resin composition is obtained by blending (A) 100 pts.wt. of a thermoplastic resin such as a polyester with (B) 0.5-100 pts.wt. of a phosphonitrile linear polymer and/or its cyclic polymer having a recurring unit of formula I [A and B each is O, N or S; R1 and R2 each is a 1-15C aryl, an alkyl, an aralkyl or a cycloalkyl; (x) and (y) each is 0 or 1; (n) is >=3] and (C) 0.5-100 pts.wt. of a salt consisting of a compound of formula II (R3 to R6 each is H, aryl, an alkyl, etc.; R is NR3R4, NR5R6, H, aryl, an alkyl, etc.) and cyanuric acid or isocyanuric acid.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition containing a non-halogen flame retardant. More specifically, it has excellent mechanical properties, does not generate harmful gas or corrosive gas, and does not deteriorate hydrolysis resistance.
The present invention relates to a flame-retardant thermoplastic resin composition suitable for electric / electronic device parts such as switches, case members, transformer members, coil bobbins, 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, 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, in this method, a large amount of smoke is generated during combustion, halogen is liberated and corrosive hydrogen halide gas is generated during processing and use of molded products, which causes corrosion of molds and metal contacts. There is a problem that it may become the source of pollution. Further, the antimony compound, which is a flame retardant aid usually used in combination to enhance the effect of the flame retardant, is a foreign substance to the resin, which causes a decrease in mechanical properties.

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 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.), polyphosphonate blends (USP-3719727), and red phosphorus blends (JP-A-49-74240). Among them, JP-A-55-5916 and JP-A-49-742
Although there is an example of an injection molding composition in Japanese Patent No. 40,
The conventional flame-retardant technology using phosphorus compounds basically targets fiber and film applications, and has not been aimed at resin molded products.

Further, a method of adding a phosphonitrile linear polymer or a cyclic polymer is disclosed in JP-A-50-48055.
JP-A-50-92950, JP-A-51-
Although disclosed in Japanese Patent No. 36266 and the like, these also mainly aim at making the fibers flame-retardant. On the other hand, Japanese Patent Application Laid-Open No. 51-91957 discloses a method of using a phosphonitrile linear polymer or a cyclic polymer for making a PBT resin molded product flame-retardant.
A large amount of metal oxide such as O3 and an inorganic filler are blended.

[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 it can no longer be used as a resin for injection molding.

(3) When the polyphosphonate is blended, the P (= 0) -O bond in the flame retardant is also easily hydrolyzed, and the hydrolysis product acts catalytically on the hydrolysis reaction of the resin itself. Therefore, the durability performance is reduced.

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

(5) The method of adding only a phosphonitrile linear polymer or a cyclic polymer has a small flame retarding effect. Therefore, if a large amount of a metal oxide such as Sb ₂ O ₃ and an inorganic filler are blended as an auxiliary agent, the heat resistance is reduced. The properties of the plastic resin, such as toughness, are significantly impaired.

As described above, there are many problems in applying the conventional technique mainly for fibers and films to injection molding.

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 thermoplastic resin injection molded product.

[0015]

The inventors of the present invention have made extensive studies in view of the above circumstances, and as a result, in injection molding applications, phosphonitrile linear polymers and / or cyclic polymers, and cyanuric acid or isocyanuric acid. The inventors have found that the combined use of a salt with the compound represented by the above formula (2) and a salt is specifically excellent in performance balance, and arrived at the present invention.

That is, the present invention provides (A) thermoplastic resin 1
0.5 to 100 parts by weight of (B) a phosphonitrile linear polymer and / or a cyclic polymer having a repeating unit of the general formula (1) per 100 parts by weight, and (C) a compound represented by the general formula (2). A flame-retardant resin composition comprising 0.5 to 100 parts by weight of a salt of cyanuric acid or isocyanuric acid.

[0017]

[Chemical 4] (However, in the above formula, A and B represent the same or different O, N and S atoms. R1 and R2 are the same or different aryl groups having 1 to 15 carbon atoms, alkyl groups, aralkyl groups or cycloalkyl groups. Represents a group, R1, R
A ring structure in which 2 are linked may be used. x and y are 0 or 1
Represents n means the number average degree of polymerization, and represents 3 or a numerical value larger than 3. )

[Chemical 5] (However, in the above formula R3, R4, R5, R6 are identical or different hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, or -CONH _2.
R is the same group as -NR3 R4 or -NR5 R6 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 referred to here shows fluidity when heated,
It is a synthetic resin that can be molded using this.
Specific examples thereof include polyester, polycarbonate, polyamide, polyphenylene oxide, polypropylene, polyethylene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene / acryl. Ethyl acid copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer and ethylene / propylene-g-maleic anhydride copolymer, polyester polyether elastomer, polyester polyester elastomer, etc. Among them, thermoplastic polyester is particularly preferably used. 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, etc., as well as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / decane dicarboxylate and polycyclohexane dimethylene terephthalate / Copolyester such as isophthalate, polyoxybenzoyl, polyoxybenzoyl / polyethylene terephthalate copolymer, 4,4′-biphenol / terephthalic acid / 4-hydroxybenzoic acid copolymer, hydroquinone / 4,4′-diphenyldicarboxylic acid Examples include liquid crystal polyesters such as acid / 4-hydroquinonebenzoic acid copolymers, among which polybutylene terephthalate and polybutylene naphtha are well balanced in mechanical properties and moldability. Over DOO, polycyclohexanedimethylene terephthalate, polyethylene naphthalate and polyethylene terephthalate is particularly preferably used.

The phosphonitrile linear polymer and / or cyclic polymer used in the present invention is an oligomer or polymer having a repeating unit represented by the above formula (1) and has a number average degree of polymerization of 3 or more. . It may be linear or cyclic, but especially cyclic 3
A monomer is preferably used. Further, it may be a mixture of straight-chain products and cyclic products in an arbitrary ratio.

The phosphonitrile linear polymer and / or cyclic polymer is generally hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene produced according to the following chemical reaction formula (5), or ring-opening polymerization of these cyclic oligomers. It can be synthesized by reacting the resulting poly (dichlorophosphazene) with a nucleophile such as an alcohol, a phenol, an amine, a thiol or a Grignard reagent by a known method.

[0020]

[Chemical 6] Specific examples of the phosphonitrile linear polymer and / or cyclic polymer in the present invention include the following examples, but the present invention is not limited thereto.

[0021]

[Chemical 7]

[Chemical 8]

[Chemical 9] Among these phosphonitrile compounds, especially the following formula (3)
Alternatively, the phosphazene trimer represented by (4) is preferably used from the viewpoint of flame retardancy.

[0022]

[Chemical 10] The addition amount of the phosphonitrile linear polymer and / or the cyclic polymer in the present invention is 0.5 to 1 with respect to 100 parts by weight of the thermoplastic resin in view of flame retardancy and mechanical properties of the molded product.
The amount is 00 parts by weight, preferably 1 to 80 parts by weight, more preferably 5 to 50 parts by weight.

The salt of cyanuric acid or isocyanuric acid used in the present invention is an adduct of cyanuric acid or isocyanuric acid with the compound represented by the general formula (2), and usually 1: 1 ( (Molar ratio), optionally an adduct having a composition of 1 to 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 above general formula (2), R3, R4, R
5, R6 are the same or different hydrogen, aryl group, alkyl group, aralkyl group, cycloalkyl group, or -C
It is ONH ₂ . Here, the aryl group has 6 to 6 carbon atoms.
Preferred are those having 15 carbon atoms, alkyl groups having 1 to 10 carbon atoms, aralkyl groups having 7 to 16 carbon atoms, and cycloalkyl groups having 4 to 15 carbon atoms. R is -NR3 R4 or -NR5 R in the above formula
The same group as 6 or independently of these, hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group,
A group selected from NH ₂ or —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. The cycloalkyl group having 4 to 15 carbon atoms is preferable.

Specific examples of R3, R4, R5 and R6 include hydrogen, phenyl group, p-toluyl group, α-naphthyl group, β-naphthyl group, methyl group, ethyl group, n-propyl group and 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, 4-methyl- Examples thereof include a 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.

As a specific example of R, 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, but 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.

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. Those having an average particle diameter of 100 μm or less are particularly preferable. When the salt has poor dispersibility, a dispersant such as tris (β-hydroxyethyl) isocyanurate may be used in combination.

The salt is used in an amount of 0.5 to 100 parts by weight, preferably 2 to 80 parts by weight, based on 100 parts by weight of the thermoplastic resin in view of flame retardancy, mechanical properties and surface appearance of the molded product.
More preferably, it is 3 to 70 parts by weight.

Further, in the present invention, a high degree of flame retardancy can be achieved by further blending a fluorine-based oligomer or polymer. The term "fluorine oligomer or polymer" means a synthetic polymer having a fluorine atom in the molecule. Among them, fluorinated polyolefin, fluorinated polyether, (fluorinated polyolefin / fluorinated polyether) copolymer, or these Polymers obtained by copolymerizing polymers with other fluorine-containing or fluorine-free polymers are preferably used in terms of flame retardancy and cost. Among these fluorine-based oligomers or polymers, polytetrafluoroethylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer, polyvinylidene fluoride, poly (fluoroethylene), ( A tetrafluoroethylene / propylene) copolymer is preferable, and polytetrafluoroethylene and a (tetrafluoroethylene / ethylene) copolymer are particularly preferable. The term "oligomer" or "polymer" as used herein means a polymer having a number average degree of polymerization of 3 or more, preferably a number average degree of polymerization of 5 or more, and more preferably a number average degree of polymerization of 10 or more.

By adding such a fluorine-based oligomer or polymer, it is possible to prevent droplet formation (drip) when the thermoplastic resin burns, and to impart high flame retardancy.

The addition amount of the fluorine-based oligomer or polymer in the present invention is usually 0.01 to 10 parts by weight based on 100 parts by weight of the thermoplastic resin (A) from the viewpoint of sufficient flame retardancy improving effect and moldability. Yes, preferably 0.05-
8 parts by weight, particularly preferably 0.1 to 5 parts by weight.

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

Specific examples of such fillers include glass fiber, carbon fiber, asbestos, potassium titanate whiskers, wollastonite, glass flakes, glass beads, talc, mica, clay, calcium carbonate, barium sulfate and titanium oxide. And aluminum oxide, and chopped strand type glass fiber is preferably used. The addition amount of these is preferably 5 to 140 parts by weight with respect to 100 parts by weight of the thermoplastic resin,
It is particularly preferably 5 to 100 parts by weight.

The phosphonitrile linear polymer and / or cyclic polymer used in the present invention has an extremely slight effect of promoting hydrolysis of the thermoplastic resin having an ester bond, as compared with other conventionally known phosphorus-based flame retardants. However, even if it is exposed to a high temperature for a long period of time, the phosphorus compound tends to be modified and accelerates the hydrolysis of the resin. In the present invention, this tendency can be prevented by using a hindered phenol-based stabilizer in combination and suppressing the modification of the phosphorus compound.
It has been found that good hydrolysis resistance is maintained over time. Examples of such stabilizers include 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 if necessary, and the preferable amount of the hindered phenol-based stabilizer added at that time is 100 parts by weight of the total composition. 0.01 to 1 part by weight, more preferably 0.03 to 0.5 part by weight.

Further, with respect to the resin composition of the present invention, phosphorus-based, sulfur-based, etc. antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, release agents, and dyes are used within the range not impairing the object of the present invention. -One or more ordinary additives such as colorants including pigments can be added.

The resin composition of the present invention is usually produced by a known method. For example, a method of melt-mixing a thermoplastic resin, a phosphonitrile linear polymer and / or a cyclic polymer, a salt of cyanuric acid or isocyanuric acid, and other necessary additives in an extruder, or a method for uniformly mixing particles And the like, and a method of molding simultaneously with mixing in an injection molding machine.

[0038]

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

(2) LOI (Limiting 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) Flame Retardancy A 1/32 inch-thick combustion test piece was prepared from pellets, and the flame retardance was evaluated according to the evaluation standard defined in UL94. Flame retardancy level is V-0>V-1>V-2> H
It decreases in the order of B.

(4) Hydrolysis resistance A 1/32 inch combustion test piece was subjected to constant temperature and high humidity at 80 ° C. and 95%.
After treatment for a predetermined time under the condition of% RH, the change in molecular weight after treatment was measured by GPC (Gel Permeation Chromatography, polystyrene conversion), 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.

(6) Number average degree of polymerization The number average degree of polymerization n of the phosphonitrile linear polymer and / or cyclic polymer was calculated from the number average molecular weight (in terms of polystyrene) measured under the following conditions using GPC.

Apparatus: Waters, Column: TSK-G
2500H / TSK-G4000H, solvent: N-methyl-2-pyrrolidone, (0.02N lithium chloride), flow rate: 0.5 mL / min, column temperature: 60 ° C., detector: UV (260 nm) Reference Example 1 Number average A dichlorophosphazene oligomer having a degree of polymerization of n = 20 was reacted with phenol in THF in the presence of triethylamine. The resulting reaction solution was evaporated to dryness, and the residue was washed with water to remove salts. Further purification was performed by washing with acetone and then ethanol. Yield 90%. The phosphonitrile linear polymer thus obtained is used as a flame retardant A
And The weight loss rate of the flame retardant A at 280 ° C. in the thermobalance was 0.8%. Further, the number average degree of polymerization n did not change and was n = 20.

Reference Example 2 A phosphonitrile linear polymer was synthesized in the same manner as in Reference Example 1 except that aniline was used instead of phenol. The yield was 88%, and the thermal loss at 280 ° C. in the thermobalance was 1.2%. This phosphonitrile linear polymer is designated as flame retardant B. There is no change in the number average degree of polymerization n
= 20.

Reference Example 3 A phosphonitrile linear polymer was synthesized in the same manner as in Reference Example 1 except that thiophenol was used instead of phenol. The yield was 80%, and the thermal loss at 280 ° C. in the thermobalance was 1.5%. This phosphonitrile linear polymer is designated as flame retardant C. The number average degree of polymerization n was unchanged and n = 20.

Reference Example 4 A phosphonitrile linear polymer was synthesized in the same manner as in Reference Example 1 except that butyl alcohol was used instead of phenol. The yield was 86%, and the loss on heat at 280 ° C. in the thermobalance was 1.2%. This phosphonitrile linear polymer is designated as flame retardant D. The number average degree of polymerization n was unchanged and n = 20.

Reference Example 5 A dichlorophosphazene oligomer having a number average degree of polymerization of n = 20 and phenylmagnesium bromide were reacted in THF. Hereinafter, it was purified in the same manner as in Reference Example 1.
The yield was 78%, and the thermal loss at 280 ° C was 1.
It was 6%. This phosphonitrile linear polymer is designated as flame retardant E. The number average degree of polymerization n does not change and n = 2.
It was 0.

Reference Example 6 Hexachlorocyclotriphosphazene (cyclic trimer) was reacted with phenol in THF in the presence of triethylamine. The resulting reaction solution was evaporated to dryness and washed with water to remove salts. Yield 95%. The phosphonitrile cyclic polymer thus obtained is used as a flame retardant F. The weight loss rate of the flame retardant F at 280 ° C in the thermobalance is 3.5%.
Met. Further, the number average degree of polymerization n did not change and n = 3.

Further, the obtained flame retardant F was purified by recrystallization with acetone. This purified product is designated as flame retardant G. Flame retardant G
The heating weight loss rate in the thermobalance was 0.6%.

Reference Example 7 A phosphonitrile cyclic polymer was synthesized in the same manner as in Reference Example 6 except that catechol was used instead of phenol. The yield was 78%, and the thermal loss at 280 ° C. in the thermobalance was 0.7%. This phosphonitrile cyclic polymer is used as a flame retardant H. There is no change in the number average degree of polymerization n
= 3.

Reference Example 8 A phosphonitrile cyclic polymer was synthesized in the same manner as in Reference Example 6 except that o-phenylenediamine was used instead of phenol. The yield was 77%, and the thermal loss at 280 ° C. in the thermobalance was 1.4%. This phosphonitrile cyclic polymer is designated as flame retardant I. The number average degree of polymerization n did not change and n = 3.

Examples 1 to 29, Comparative Examples 1 to 19 Various kinds of the compounds shown in Tables 1, 2 and 5 were added to 100 parts by weight of polybutylene terephthalate having an intrinsic viscosity of 0.85 (25 ° C., o-chlorophenol solution). A phosphorus compound, a salt of cyanuric acid or isocyanuric acid, and other additives are mixed, and a resin temperature of 26 mm is obtained by using a 30 mmΦ biaxial extruder.
Melt extruded at 0 ° C. After the obtained pellets were dried, a tensile test piece specified in ASTMD-638 and a flame retardant evaluation sample based on UL94 were prepared by injection molding (mold temperature: 80 ° C.). In addition, press molding was performed to prepare a sample for LOI measurement.

Table 3 shows the measurement results of LOI, flame retardancy, mechanical properties, color tone of molded articles, and hydrolysis resistance of each sample.
It shows collectively in 4 and 6.

The compounding amounts of the phosphonitrile linear polymer or cyclic polymer and various phosphorus-based flame retardants are also described in addition to the number of parts and the weight percentage of phosphorus in the composition.

The antioxidant (hindered phenolic stabilizer) in the table means pentaerythrutyl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Ciba. Geigy's "IR-
1010 "), and the flame retardant J is commercially available P (= O)-
It is a resorcinol type bisphosphate (“Phosflex 574” manufactured by Akzo Japan) having an O bond, and the fluoropolymer is polytetrafluoroethylene (“Polyflon TFEF10” manufactured by Daikin Industries, Ltd.).
4 ").

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

[0061]

[Table 4]

[0062]

[Table 5]

[0063]

[Table 6]

Examples 1-8, 11-13, 15, 16,
Based on the LOI values of 18, 19, 21, 22 and Comparative Examples 1 and 2 and the evaluation results based on UL94, excellent flame retardancy was obtained by blending a phosphonitrile linear polymer or cyclic polymer and cyanurate with a polyester resin. You can see that it can be added. In addition, in Examples 9, 10, 14,
According to 17, 20, 23 and Comparative Example 3, the same can be said when reinforced with glass fiber.

Further, from Examples 1 to 23 and Comparative Examples 7 to 14, when phosphonitrile linear polymer or cyclic polymer and cyanuric acid salt were blended, mechanical properties of polyester such as red phosphorus and phosphoric acid ester, Crystallization characteristics, color tone and hydrolysis resistance are not significantly deteriorated.

Further, from Examples 1 to 23 and Comparative Examples 4 to 6, excellent flame retardancy was not obtained when only the cyanuric acid salt was blended with the polyester, and it was used in combination with the phosphonitrile linear polymer or cyclic polymer. It can be seen that excellent flame retardancy is imparted only by doing so. Similarly, sufficient flame retardancy cannot be obtained by blending only the phosphonitrile linear polymer or cyclic polymer, and excellent flame retardancy can be imparted by using together with cyanuric acid salt.
9 and 16 to 17 and Comparative Examples 15 to 18 (LOI
Although the difference in value is not large, a marked difference is observed in the evaluation based on UL94).

When the phosphonitrile linear polymer or cyclic polymer of the present invention is blended with the polyester, the hydrolysis resistance is not so much decreased, but it is certainly a little as compared with the polyester containing no flame retardant. Decrease (for example, Examples 3, 5, and 7 and Comparative Examples 1 and 2).
However, it can be seen that the addition of the hindered phenolic stabilizer improves the hydrolysis resistance and shows the hydrolysis resistance close to the level of the polyester containing no flame retardant (Examples 7 and 8, Examples 12 and 13, Examples 15 and 16, Examples 18 and 19, Examples 21 and 2
2). A similar trend is seen with glass fiber reinforced systems (Examples 9 and 10).

In Examples 6 and 8, the effect of the presence or absence of purification on the physical properties of polyester was investigated for phosphonitrile cyclic polymers reacted with phenol. It can be seen that the mechanical properties, color tone and hydrolysis resistance of Example 8 using the purified phosphonitrile cyclic polymer are slightly improved as compared with Example 6 using the unpurified one, but the flame retardancy. You can see that there is no big difference in.

Further, in Examples 24 to 29 of the present invention, the addition of the fluorine-based polymer achieves a higher flame retardancy in which no melt dripping (drip) occurs in the burning test based on UL-94. The same is also true for glass fiber reinforced systems (Examples 26 and 29).

Examples 30 to 35, Comparative Examples 20 to 31 The polystyrene reduced weight average molecular weight measured by GPC was 5
1000 bisphenol A type polycarbonate, GP
The polystyrene reduced weight average molecular weight measured by C is 120.
000 poly (2,6-dimethyl-1,4-phenylene) oxide and polystyrene having a weight average molecular weight of 430000 (weight ratio 60/40, hereinafter abbreviated as PPO), relative viscosity 2.70 (25 ° C., 1 % Concentrated sulfuric acid solution) nylon 6, and 100 parts by weight of each are mixed with a phosphorus compound such as a phosphonitrile compound shown in Table 7, a salt of cyanuric acid or isocyanuric acid, and other additives, and 30 mmΦ biaxial extrusion is performed. It was melt extruded using a machine. The resulting pellets are injection molded to ASTM D-6
Samples for flame retardancy evaluation were prepared based on the tensile test pieces specified in No. 38 and UL94. In addition, press molding was performed to prepare a sample for LOI measurement.

Table 8 shows the measurement results of LOI, flame retardancy, mechanical properties, color tone of molded articles, hydrolysis resistance and the like of each sample.

The amounts of the phosphonitrile linear polymer or cyclic polymer and various phosphorus-based flame retardants to be compounded are also described in addition to the number of parts and the weight% of phosphorus in the composition.

[0073]

[Table 7]

[0074]

[Table 8]

From the LOI values of Examples 30 and 31 and Comparative Example 20 and the evaluation results based on UL94, it is understood that excellent flame retardancy can be imparted by adding a phosphonitrile compound and a cyanuric acid salt to a polycarbonate resin. The same applies when reinforced with glass fiber. Further, from Comparative Examples 21 and 22, it can be seen that high flame retardancy cannot be obtained by blending only the phosphonitrile compound or only the cyanuric acid salt. In Comparative Example 23, red phosphorus was used instead of the phosphonitrile compound, but high flame retardancy was not obtained, and reduction in hydrolysis resistance was also observed.

From the LOI values of Examples 32 and 33 and Comparative Example 24 and the evaluation results based on UL94, it is understood that excellent flame retardancy can be imparted by blending the phosphonitrile compound and the cyanuric acid salt in the PPO resin. The same applies when reinforced with glass fiber. Further, from Comparative Examples 25 and 26, it can be seen that high flame retardancy cannot be obtained by blending only the phosphonitrile compound or only the cyanuric acid salt. In Comparative Example 27, red phosphorus was used instead of the phosphonitrile compound, but high flame retardancy was not obtained.

From the LOI values of Examples 34 and 35 and Comparative Example 28 and the evaluation results based on UL94, it is understood that excellent flame retardancy can be imparted by blending the phosphonitrile compound and the cyanuric acid salt with the polyamide resin.
The same applies when reinforced with glass fiber. Furthermore, from Comparative Examples 29 and 30, only the phosphonitrile compound,
Alternatively, it can be seen that high flame retardancy cannot be obtained with a combination of cyanuric acid salt alone. In Comparative Example 31, red phosphorus was used instead of the phosphonitrile compound, but high flame retardancy was not obtained.

[0078]

【The invention's effect】

(1) The combined use of the phosphonitrile linear polymer or cyclic polymer of the present invention and a salt of cyanuric acid or isocyanuric acid exhibits a higher flame retarding effect than other conventionally known phosphorus-based flame retardants. Furthermore, it is an excellent flame-retardant formulation that does not generate volatile substances during resin processing and has no P (= O) -O bond, and thus has good hydrolysis resistance and does not adversely affect the thermoplastic resin.

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

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Claims (10)

[Claims] 1. A phosphonitrile linear polymer and / or cyclic polymer having a repeating unit of (B) general formula (1) and / or a cyclic polymer of 0.5 to 100 parts by weight of (A) a thermoplastic resin.
A flame-retardant resin composition comprising 100 parts by weight and 0.5 to 100 parts by weight of a salt of (C) a compound represented by the general formula (2) and cyanuric acid or isocyanuric acid. [Chemical 1] (However, in the above formula, A and B represent the same or different O, N and S atoms. R1 and R2 are the same or different aryl groups having 1 to 15 carbon atoms, alkyl groups, aralkyl groups or cycloalkyl groups. Represents a group, R1, R
A ring structure in which 2 are linked may be used. x and y are 0 or 1
Represents n means the number average degree of polymerization, and represents 3 or a numerical value larger than 3. ) [Chemical 2] (However, in the above formula R3, R4, R5, R6 are identical or different hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, or -CONH _2.
R is the same group as -NR3 R4 or -NR5 R6 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, which further comprises 0.01 to 10 parts by weight of a fluorine-based oligomer or polymer based on 100 parts by weight of the thermoplastic resin. 3. Glass fiber, glass flakes, glass beads, carbon fibers, asbestos, potassium titanate whiskers, wollastonite, talc, mica, clay, calcium carbonate, barium sulfate, titanium oxide per 100 parts by weight of the thermoplastic resin. , 1 selected from aluminum oxide
The flame-retardant resin composition according to claim 1, further comprising 5 to 140 parts by weight of one or more kinds of fillers. 4. The phosphonitrile linear polymer and / or
Alternatively, the cyclic polymer (B) is a cyclic trimer.
The flame-retardant resin composition described. 5. The phosphonitrile linear polymer and / or
Alternatively, the cyclic polymer (B) is represented by the following formula (3) or (4)
The flame-retardant resin composition according to claim 1, which is a cyclic trimer represented by: [Chemical 3] 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 2, wherein the fluorine-based oligomer or polymer is polytetrafluoroethylene. 8. The filler is glass fiber.
The flame-retardant resin composition described. 9. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin is a thermoplastic polyester. 10. A hindered phenol-based stabilizer 0.0
The flame-retardant resin composition according to claim 1 or 2, further comprising 1 to 1 part by weight.