JP3484802B2 - Flame retardant polymer composition and molded article - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant polymer composition and a molded article using a non-halogen flame retardant.
More specifically, it has excellent mechanical properties and does not deteriorate hydrolysis resistance, and it can be used for connectors, relays, switches, case members,
Electrical and electronic equipment parts such as transformer members and coil bobbins,
The present invention relates to a flame-retardant polymer composition suitable for automobile parts and machine parts, and a molded article obtained by molding the same.

[0002]

2. Description of the Related Art Polyester represented by polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexane dimethylene terephthalate and the like, or thermoplastic polymers such as polycarbonate, polyamide and polyphenylene oxide are
Taking advantage of its excellent 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, since these thermoplastic polymers are inherently flammable, in order to use them as industrial materials, in addition to the general balance of chemical and physical properties, safety against flames, that is, flame retardancy is required. In many cases.

As a method of imparting flame retardancy to a thermoplastic polymer, a method of compounding a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant aid is generally used. 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 for flame-retarding a thermoplastic polymer 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 flame-retarding a thermoplastic polyester, copolymerization of a phosphonic acid unit or a phosphinic acid unit with polyester (Japanese Patent Laid-Open Nos. 51-54691 and 50-5).
No. 6488), copolymerization of a monomer having a cyclic phosphinite skeleton as a pendant (JP-A-52-98089).
JP-A-55-5916, JP-A-60-2
40755), 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 applications, and is not intended for molded articles, films or sheets. .

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 JP-A 8-90348, JP-A-48-91147, JP-A-52-102255, etc., these are also mainly aimed at flame retardation in fibers. On the other hand, European Patent Publication EP491986 discloses a method of adding a resorcin type aromatic phosphate oligomer for flame retarding a polybutylene terephthalate (PBT) type alloy molded article. A method of adding a resorcin-type aromatic bisphosphate, melamine cyanurate and an inorganic filler is disclosed.

[0007]

A flame-retardant polymer composition for use in molded articles such as injection molding, film applications, sheet applications, etc., has mechanical properties of molded articles, and the molded articles are used under high temperature and high humidity conditions. Heat resistance and hydrolysis resistance are required to maintain reliability even when the above is performed. 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 phosphorus-containing monomer is copolymerized, particularly when polyester is used, a large amount of copolymerization rate is obtained when it is attempted to obtain the level of flame retardancy required for electric / electronic parts, and the melting point and crystallization rate of the polymer itself are increased. Is significantly reduced, and its use as an injection molding polymer is extremely limited. (3) In the blend of red phosphorus, there are problems such as deterioration of mechanical properties of the thermoplastic polymer and coloring, and the flame retarding effect on the thermoplastic polymer is small. (4) In a blend of resorcin-type aromatic phosphate and resorcin-type aromatic phosphate oligomer, these phosphates are easily hydrolyzed, and the hydrolysis product acts catalytically on the hydrolysis reaction of the resin itself, which deteriorates the durability performance. . In addition, when a polymer composition containing a resorcin-type aromatic phosphate or a resorcin-type aromatic phosphate oligomer is used as a molded article, a bleeding phenomenon is observed in which these compounds exude to the surface of the molded article.

As described above, there are many problems in applying the conventional technique mainly for fibers 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 specific thermoplastic polymer, and at the same time has good moldability, hydrolysis resistance and mechanical properties. An object of the present invention is to obtain a flame-retardant polymer composition and a molded article thereof which can give a molded article such as a good thermoplastic polymer molded article, sheet or film.

[0010]

The inventors of the present invention have made extensive studies in view of the above circumstances, and as a result, have found that hydroquinone having a specific degree of polymerization is used in molded article applications such as injection molding applications, sheet applications, and film applications. The present invention has been accomplished by finding that a type aromatic oligophosphate or polyphosphate is a flame retardant having a particularly excellent performance balance.

That is, the present invention relates to a phenoxy resin, a poly
Phenylene oxide, modified polyphenylene oxide,
One or more kinds selected from Li phenylene sulfide
A flame-retardant polymer composition comprising a thermoplastic polymer which is a mixture of the above and a thermoplastic polyester and a flame retardant having a structure represented by the general formula (1).

[0012]

[Chemical 17]

(However, in the above formula, R ¹ , R ² , R ³ ,
R ⁴ is the same or different hydrogen atom or has 1 to 1 carbon atoms.
5 represents an alkyl group. Ar ¹ , Ar ² , Ar ³ , A
r ⁴ represents the same or different phenyl group or a phenyl group substituted with a halogen-free organic residue.
In addition, n represents the number average degree of polymerization, and n is 0.5 or more and 40 or more.
Is less than. 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. ) The thermoplastic polymer referred to herein is a mixture of phenoxy resin, polyphenylene oxide, modified polyphenylene oxide, and one or more thermoplastic polyesters selected from polyphenylene sulfide. Specific examples of the thermoplastic polyester include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycyclohexane dimethylene terephthalate and polyethylene-1,2-bis (phenoxy) ethane-4,4. '-Dicarboxylate, polyethylene isophthalate / terephthalate,
Examples include copolymerized polyesters such as polybutylene terephthalate / isophthalate, polybutylene terephthalate / decane dicarboxylate and polycyclohexane dimethylene terephthalate / isophthalate.
Of these, polybutylene terephthalate, polybutylene naphthalate, polycyclohexane dimethylene terephthalate, with well-balanced mechanical properties and moldability,
Polyethylene naphthalate and polyethylene terephthalate are particularly preferably used. In addition, the blending ratio of the thermoplastic polyester and one or a mixture of two or more selected from phenoxy resin, polyphenylene oxide, modified polyphenylene oxide, and polyphenylene sulfide is 100 to 100 parts by weight of the thermoplastic polyester. Parts by weight are preferred.

The flame retardant hydroquinone type aromatic oligophosphate or aromatic polyphosphate used in the present invention is a compound having a repeating unit represented by the above formula (1), in which k and m are respectively 0 or more 2
The following integers and k + m are integers 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.

The flame retardant hydroquinone type aromatic oligophosphate or aromatic polyphosphate used in the present invention is a compound having a repeating unit represented by the above formula (1), and its number average degree of polymerization is 0.5. It is preferably not less than 40 and less than 40, preferably 0.5 to 20, particularly preferably 0.8 to 15. The average degree of polymerization is a value measured by GPC (Gel Permeation Chromatography, polystyrene conversion). Further, from the viewpoint of flame retardancy, those having a number average degree of polymerization of 1 to 2.5 are preferable.

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 ethyl 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 a halogen-free organic residue. 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, and a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a naphthyl group are preferable. Especially, a phenyl group, a tolyl group and a xylyl group are preferable.

The aromatic oligophosphate or aromatic polyphosphate is generally produced according to the following chemical reaction formula (4) or (5). When synthesizing according to the formulas (4) and (5), 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 degree of polymerization of the entire phosphate mixture is not less than 0.5.

[0019]

[Chemical 18]

Specific examples of the aromatic oligophosphate or aromatic polyphosphate in the present invention include the followings, but the invention is not limited thereto.

[0021]

[Chemical 19]

[0022]

[Chemical 20]

[0023]

[Chemical 21]

[0024]

[Chemical formula 22]

[0025]

[Chemical formula 23]

[0026]

[Chemical formula 24]

[0027]

[Chemical 25]

[0028]

[Chemical formula 26]

[0029]

[Chemical 27]

Of these aromatic oligophosphates or aromatic polyphosphates, Ar ¹ , Ar ² and A
It is preferable that r ³ and Ar ⁴ are the same or different phenyl, tolyl, or xylyl groups, and k and m are each 1. In particular, the aromatic oligophosphate or polyphosphate represented by the following formula (2) is flame-retardant. It is preferably used from the viewpoints of properties, mechanical properties, and economic efficiency.

[0031]

[Chemical 28]

In the present invention, the amount of aromatic oligophosphate or aromatic polyphosphate added is 0.5 to 100 parts by weight, preferably 1 to 100 parts by weight from 100 parts by weight of the thermoplastic polymer in view of flame retardancy and mechanical properties. 80 parts by weight, more preferably 5 to 50 parts by weight.

The flame retardancy of polymer compositions is determined by the phosphorus content of the composition. Therefore, in the case of a high phosphorus content aromatic oligophosphate or aromatic polyphosphate, a sufficiently high flame retardancy can be achieved with a small amount of the compound, but a low phosphorus content aromatic oligophosphate or aromatic polyphosphate can be obtained. In some cases, a large amount of compound is required. The phosphorus content (phosphorus content in the composition) required for flame retarding the thermoplastic polymer composition is usually 0.1 to 10
%, Preferably 0.2 to 8%, particularly preferably 0.5 to
5%.

By further adding a salt of the triazine derivative represented by the general formula (3) and cyanuric acid and / or isocyanuric acid to the flame-retardant polymer composition of the present invention, higher flame retardancy is obtained. Sex can be achieved.

[0035]

[Chemical 29]

(However, in the above formula, R ⁵ , R ⁶ , R ⁷ ,
R ⁸ is the same or different hydrogen, aryl group, alkyl group, aralkyl group, cycloalkyl group, or -CON
H ₂ . R is -NR ⁵ R ⁶ or-in the above formula.
It is the same group as NR ⁷ R ⁸ or independently of these, a group selected from hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, —NH ₂ or —CONH ₂ . The molar ratio of the triazine derivative represented by the general formula (3) to cyanuric acid and / or isocyanuric acid is usually 1: 1 and in some cases 1: 2. Of the triazine derivatives represented by the general formula (3), those that do not form a salt with cyanuric acid or isocyanuric acid are excluded.

In the general formula (3), 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
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 —NR ⁵ R ⁶ or —NR ⁷ R in the above formula
^The same group as ⁸ or independently of them, 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 R ⁵ , R ⁶ , R ⁷ and R ⁸ include 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 triazine derivative represented by the general formula (3) with cyanuric acid or isocyanuric acid, melamine, benzoguanamine, acetoguanamine, 2-amide-4,6-diamino-1,3,5 are particularly preferable. -Triazine, mono (hydroxymethyl) melamine, di (hydroxymethyl) melamine, tri (hydroxymethyl)
Salts of melamine are preferred, especially salts of melamine, benzoguanamine, acetoguanamine.

As the salt of the triazine derivative represented by the general formula (3) with cyanuric acid or isocyanuric acid, a mixture of the triazine derivative represented by the general formula (3) and cyanuric acid or isocyanuric acid is prepared as an aqueous slurry. It is a powder obtained by thoroughly mixing and forming fine particles of both salts, and then filtering and drying this slurry, which is different from a simple mixture. This salt does not have to be completely pure, and the unreacted compound represented by the formula (3), cyanuric acid, or isocyanuric acid may remain. The form of this salt is not particularly limited, but it is preferable to use a salt obtained as fine powder as possible from the viewpoint of mechanical strength and surface property of a molded article obtained from the composition of the present invention. . From the viewpoint of flame retardancy and mechanical properties, the smaller the average particle diameter in the composition, the better, and it is particularly preferable that the average particle diameter be 100 μm or less. Also,
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 0.5 to 100 parts by weight, preferably 2 to 80 parts by weight, more preferably 100 parts by weight of the thermoplastic polymer in view of flame retardancy, mechanical properties and surface appearance. 3 to 70 parts by weight.

If the fluorine-containing polymer is further added to the flame-retardant polymer composition of the present invention, the drop (drip) of droplets during combustion is suppressed. As such a fluorine-based polymer, 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. However, among them, polytetrafluoroethylene, (tetrafluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer,
Polyvinylidene fluoride is preferable, and polytetrafluoroethylene and (tetrafluoroethylene / ethylene) copolymer are particularly preferable.

The amount of the fluoropolymer added is usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 100 parts by weight of the thermoplastic polymer in view of mechanical properties and moldability. Is 0.2 to 3 parts by weight.

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

The aromatic oligophosphate or aromatic polyphosphate used in the present invention has an action of promoting hydrolysis of a thermoplastic polymer having a dehydration condensation type structure such as an ester bond, as compared with other conventionally known phosphorus flame retardants. It was found to be extremely slight, but when a hindered phenol stabilizer was also used in combination, very good hydrolysis resistance was maintained even when exposed to high temperatures for a long period of 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-hydrocinnamamide), N, N′-trimethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) 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 100 parts by weight of the thermoplastic polymer. For 0.01 to
3 parts by weight, preferably 0.01 to 1 part by weight, more preferably 0.03 to 0.5 part by weight.

Further, with respect to the flame-retardant polymer composition of the present invention, phosphorus-based, sulfur-based, etc. antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, release agents are used within the 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.

By further adding a fibrous and / or granular filler to the flame-retardant polymer composition of the present invention, strength, rigidity, heat resistance, etc. can be greatly 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 5 to 100 parts by weight of the thermoplastic polymer.
It is preferably 140 parts by weight, particularly preferably 5 to 100 parts by weight.

The flame-retardant polymer composition of the present invention is generally produced by a known method. For example, a method of melt-mixing a thermoplastic polymer with an aromatic oligophosphate or aromatic polyphosphate, and other necessary additives in an extruder, or after mechanically mixing particles together in a molding machine. Examples include a method of molding simultaneously with mixing.

The flame-retardant polymer composition of the present invention is injection molded,
It can be molded into an injection-molded article of any shape, a molded article such as an extrusion molded article, or a molded article such as a sheet or a film by a generally known method such as extrusion molding and compression molding.

[0053]

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 ASTM
Tensile yield strength and breaking elongation were measured according to D-638. (2) LOI (Limited Oxygen Concentration Index) A 150 mm x 6 mm x 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 x 12.7 mm x 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. Flame retardancy level is V-0
It decreases in the order of>V-1>V-2> 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 the structures of the aromatic phosphate compounds used in Examples and Comparative Examples are shown below.

[0054]

[Chemical 30]

[0055]

[Chemical 31]

[0056]

[Chemical 32]

The number average molecular weight and the number average degree of polymerization n of the above compound were as follows. A: 600 (n = 0.88) B: 680 (n = 1.19) C: 720 (n = 1.12) D: 700 (n = 1.20) E: 3400 (n = 10.98) F: 810 (n = 1.38) G: 687 (n = 1.00) H: 1240 (n = 1.00) I: 580 (n = 1.02) J: 600 (n = 1.04) K: 660 (n = 1.11) The above number average molecular weight is measured by GPC. It is a value measured under the conditions shown. Device: Waters, Column: TSK-G2500H /
TSK-G4000H solvent: NMP (0.02N lithium chloride), flow rate:
0.5 mL / min, Detection: UV (260 nm) In Examples 1 to 28 Contact and Comparative Example 1-1 6,19～3
When the salt of cyanuric acid used in 7 was 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. Real施例1-1 4 intrinsic viscosity of 0.85 (25 ℃, o- chlorophenol dissolved
Liquid) polybutylene terephthalate measured by GPC
The polystyrene-converted weight average molecular weight is 59000
Phenoxy resin (bisphenol A and epichlorohydric
Condensate with benzene, referred to as phenoxy in the table), GP
The polystyrene reduced weight average molecular weight measured by C is 120.
Of poly (2,6-dimethyl-1,4-phenylene)
Oxide) (hereinafter abbreviated as PPO), melt viscosity 800 po
Az (320 ℃, shear rate 1000 / sec) linear tie
Polyphenylene sulfide (hereinafter abbreviated as PPS),
Phosphorus compounds such as aromatic phosphate compounds, cyanu
Acid or isocyanuric acid salts and other additives
Are blended in the ratio shown in Table 1, and a 30 mmΦ twin-screw extruder is used.
And melt extruded. Injection molding the resulting pellets
Fabrication of tensile test pieces specified in ASTM D-638
did. In addition, the LOI measurement sump is performed by press molding.
And flame retardant evaluation samples based on UL94
It was

The LOI, flame retardancy and mechanical characteristics of each sample
Table 2 shows the measurement results of the properties, color tone of molded products, hydrolysis resistance, etc.
Shown together.

The aromatic phosphate compound and each
Regarding the blending amount of the phosphorus-based flame retardant, in addition to the number of parts,
The weight% of phosphorus in the mixture is also described. Well
In addition, the antioxidant in the table means pentaerythrutyl-tetra
Kiss [3- (3,5-di-t-butyl-4-hydroxy
(Phenyl) propionate] (Ciba Geigy "I"
R-1010 "). GF is a glass fiber.
Forget

[0060]

[Table 1]

[0061]

[Table 2]

Examples 1, 3, 5, 7, 9, 11, 13
Based on the LOI value and the evaluation result based on UL94,
Ter resin mixed with phenoxy resin, PPO, PPS
Aromatic phosphate and cyanuric acid salt
It has been found that excellent flame retardancy can be imparted by blending it.
Light Further, Examples 2, 4, 6, 8, 10, 12, 14
The same can be said when reinforced with glass fiber.
It In addition, Comparative Examples 20, 23 to 27, 30 to 3 described later
7 is compared with Examples 1 to 14, the polyester resin single
Mixing with phenoxy resin, PPO, PPS than in the case of Germany
It can be seen that the product has better flame retardancy and mechanical properties. Examples 15-28 Polyflon MPA FA-100 (Poly
Tetrafluoroethylene down powder) further added 0.3 part by weight
Exactly the same resin composition as in Examples 1 to 14 except that
Was prepared. LOI, flame retardancy, mechanical characteristics of each sample
Table 3 shows the results of measurement of the properties, color tone of molded products, hydrolysis resistance, etc.
Shown together.

[0063]

[Table 3]

The compositions of Examples 15 to 28 were all V-
Shows 0 level flame retardancy, and drops liquid drops during the combustion test.
I couldn't see the bottom (drip). Also, mechanical properties,
The color tone and hydrolysis resistance of the molded product are the same as in Examples 1-14.
It was from Bell. Comparative Examples 1-37 Intrinsic viscosity 0.85 (25 ° C, o-chlorophenol soluble
Liquid polybutylene terephthalate (hereinafter abbreviated as PBT)
Be) the species Li shown in Tables 4 and 5 with respect to 100 parts by weight
Compounds, salts of cyanuric acid or isocyanuric acid
And other additives are mixed, and a 30mmΦ twin-screw extruder is used.
It was melt extruded at a resin temperature of 260 ° C. Obtained Pele
AS after being dried by injection molding (mold temperature 80 ° C)
A tensile test piece specified in TMD-638 was prepared.
It was Samples for LOI measurement by press molding
And flame retardant evaluation sample based on UL94
It was

The LOI, flame retardancy and mechanical characteristics of each sample
Table 6 and Table 6 show the measurement results of the properties, color tone of molded products, and hydrolysis resistance.
And 7 are shown collectively.

The aromatic phosphate compound and each
Regarding the blending amount of the phosphorus-based flame retardant, in addition to the number of parts, the composition
The weight% of phosphorus in the mixture is also described.

[0067]

[Table 4]

[0068]

[Table 5]

[0069]

[Table 6]

[0070]

[Table 7]

[0071]

(1) The aromatic (poly) phosphate used in the present invention exhibits a higher flame retarding effect than other conventionally known phosphorus flame retardants, and is used in combination with a salt of cyanuric acid or isocyanuric acid. Shows a higher flame retarding effect.
Further, it is an excellent flame retardant formulation which has good hydrolysis resistance and does not adversely affect the properties of the thermoplastic resin. (2) The flame-retardant polymer composition obtained by the present invention is not only good in flame retardancy but also excellent in mechanical properties, melt flowability and surface appearance, and hydrolysis resistance is not deteriorated. It is useful as parts, electric parts and automobile parts. (3) Practical injection-molded articles, extrusion-molded articles, and other molded articles, films, sheets, etc. that are excellent in flame retardancy and hydrolysis resistance by molding the flame-retardant polymer composition obtained by the present invention. Molded articles can be obtained.

[0072]

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI C08L 71/10 C08L 71/10 71/12 71/12 81/02 81/02 101/00 101/00 (56) References Kaihei 7-157595 (JP, A) JP 7-166073 (JP, A) JP 7-196843 (JP, A) JP 7-233311 (JP, A) JP 5-1079 ( JP, A) JP 5-70671 (JP, A) JP 3-281652 (JP, A) JP 4-227951 (JP, A) JP 48-91147 (JP, A) JP 50-504421 (JP, A) JP 59-179556 (JP, A) JP 60-47056 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 1 / 00-101/16 C08K 3/00-13/08

Claims (18)

(57) [Claims] 1. A phenoxy resin, polyphenyleneoxy
, Modified polyphenylene oxide, polyphenylene sulphate
One or more selected from Fido and thermoplastic poly
A flame-retardant polymer composition comprising a thermoplastic polymer which is a mixture with an ester and a flame retardant having a structure represented by the general formula (1). [Chemical 1] (However, in the above formula, R ¹ , R ² , R ³ , and R ⁴ represent the same or different hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are the same or different. It represents a different phenyl group or a phenyl group substituted with a halogen-free organic residue, and n represents a number average degree of polymerization, and n is 0.5 or more and less than 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. ) 2. A flame retardant having a structure represented by the general formula (1), wherein k and m in the general formula (1) are 1 respectively.
The flame-retardant polymer composition according to claim 1, which is a flame retardant having a structure of 3. A flame retardant having a structure represented by the general formula (1) is Ar ¹ , Ar ² , or A in the general formula (1).
The flame-retardant polymer composition according to claim 1, wherein r ³ and Ar ⁴ are flame retardants having a structure in which phenyl, tolyl or xylyl groups are the same or different. 4. A structure having a structure represented by the general formula (1) :
The flame retardant polymer composition according to claim 1, wherein the flame retardant has a structure in which n in the general formula (1) is 1 to 2.5. 5. The flame-retardant polymer composition according to claim 1, wherein the flame retardant having a structure represented by the general formula (1) is a flame retardant having a structure represented by the general formula (2). [Chemical 2] 6. The flame-retardant polymer composition according to claim 1, which contains 0.5 to 100 parts by weight of a flame retardant with respect to 100 parts by weight of the thermoplastic polymer. 7. A contract wherein the flame retardant is selected from the following :
The flame-retardant polymer composition according to claim 1. [Chemical 3] [Chemical 4] [Chemical 5] [Chemical 6] [Chemical 7] [Chemical 8] [Chemical 9] [Chemical 10] [Chemical 11] (However, in the above formula, n represents the number average degree of polymerization, and n is 0.5 or more and less than 40.) 8. A contract wherein the flame retardant is selected from the following
Motomeko 1 flame retardant poly Ma composition. [Chemical 12] [Chemical 13] [Chemical 14] (However, in the above formula, n represents the number average degree of polymerization, and n is 0.5 or more and less than 40.) 9. The flame-retardant polymer composition according to claim 1, which further comprises a triazine derivative represented by the general formula (3) and a salt of cyanuric acid and / or isocyanuric acid. [Chemical 15] (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 . ) 10. A triazine derivative and cyanuric acid and / or
Alternatively, the content of the salt of isocyanuric acid is 1
The flame-retardant polymer composition according to claim 9, which is 0.5 to 100 parts by weight with respect to 00 parts by weight. 11. The flame-retardant polymer composition according to claim 9, wherein the average particle size in the composition of the salt consisting of the compound represented by the general formula (3) and cyanuric acid and / or isocyanuric acid is 100 μm or less. object. 12. The flame-retardant polymer composition according to claim 9, wherein the compound represented by the general formula (3) is melamine. 13. The flame-retardant polymer composition according to claim 1, which further comprises 0.01 to 10 parts by weight of a fluoropolymer, based on 100 parts by weight of the thermoplastic polymer. 14. The flame-retardant polymer composition according to claim 1, further comprising 0.01 to 3 parts by weight of a hindered phenolic stabilizer based on 100 parts by weight of the thermoplastic polymer. 15. The flame-retardant polymer composition according to claim 1, which further comprises 5 to 140 parts by weight of a filler with respect to 100 parts by weight of the thermoplastic polymer. 16. A phenoxy resin, polyphenyleneoxy
, Modified polyphenylene oxide, polyphenylene sulphate
One or more selected from Fido and thermoplastic poly
A molded article obtained by molding a flame-retardant polymer composition comprising a thermoplastic polymer which is a mixture with an ester and a flame retardant having a structure represented by the general formula (1). [Chemical 16] (However, in the above formula, R ¹ , R ² , R ³ , and R ⁴ represent the same or different hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are the same or different. It represents a different phenyl group or a phenyl group substituted with a halogen-free organic residue, and n represents a number average degree of polymerization, and n is 0.5 or more and less than 40.
Further, k and m are integers of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less. ) 17. The molded article is an injection molded article.
A shaped article as described. 18. The molded article according to claim 16, wherein the molded article is a sheet or a film.