JPH11335531A - Flame-retardant reinforced polybutylene terephthalate resin composition and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant reinforced PBT resin composition having excellent or high injection moldability and giving a molding having excellent mechanical properties, impact resistance, tracking resistance and flame retardancy and containing a non-halogen flame retardant and to obtain a molding including an insert molding. SOLUTION: Provided is a flame-retardant reinforced PBT (polybutylene terephthalate) resin composition containing (A) 100 pts.wt. PBT resin, (B) 1-200 pts.wt. PET (polyethylene terephthalate) resin, (C) 0.1-50 pts.wt. red phosphorus, (D) 1-100 pts.wt. polyethylene and/or ethylene copolymer, (E) 0-100 pts.wt. salt comprising a triazine compound and cyanuric acid or isocyanuric acid, (F) 1-200 pts.wt. fibrous reinforcement, (G) 0-30 pts.wt. inorganic layered compound, (H) 0-10 pts.wt. fluoro resin, (I) 0-30 pts.wt. lubricant, (J) 0-50 pts.wt. carbon black, and (K) 0-10 pts.wt. hindered phenol stabilizer and/or phosphite stabilizer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant reinforced polybutylene terephthalate resin composition using a non-halogen flame retardant and a molded article. More specifically, excellent mechanical properties, impact resistance, tracking resistance and flame retardancy,
The present invention relates to a flame-retardant reinforced polybutylene terephthalate resin composition and molded article suitable for electric / electronic parts such as automobile parts, connectors, and mechanical parts.

[0002]

2. Description of the Related Art Polybutylene terephthalate resin (PB)
T) is utilized in a wide range of fields such as mechanical mechanism parts, electric / electronic parts, and automobile parts by utilizing its excellent characteristics.

[0003] Further, by combining PBT with a fiber reinforcing material, it is widely used as a material having further excellent mechanical properties and heat resistance. Among the fiber reinforcements, glass fibers are particularly used.

Since PBT is inherently flammable, it has not only a balance of general chemical and physical properties but also a safety against a flame due to carbonization of a component surface and a terminal contact portion, that is, a tracking resistance. Often flame retardancy is required.

[0005] In addition to the above-mentioned flame retardancy, a material which is less likely to crack when inserting the terminal, a material which is resistant to external impact, and a material which is durable and has excellent mechanical properties and impact resistance is used for parts into which metal is inserted. Is required.

As a method for imparting flame retardancy to PBT,
In general, a method of compounding a resin with a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant aid is used. However, this method tends to generate a large amount of smoke during combustion.

Therefore, in recent years, it has been strongly desired to use a flame retardant containing no halogen at all.

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

On the other hand, as a method for making a thermoplastic resin flame-retardant without using such a hydrated metal compound, adding red phosphorus is disclosed in JP-A-51-150553 and JP-A-5-150553.
JP-A-8-108248, JP-A-59-81351, JP-A-5-78560, JP-A-5-2871
No. 19, JP-A-5-295164, JP-A-5-295164
It is disclosed in Japanese Patent Application Laid-Open No. 320486 and Japanese Patent Application Laid-Open No. 5-339417. However, although any of the resin compositions is a useful flame-retardant resin material that does not use a halogen-based flame retardant, these molded articles have reduced mechanical properties, impact resistance or tracking resistance. Had issues.

In addition, by blending a polyethylene resin or a polyolefin copolymer with a halogen-based flame retardant,
As a method for improving the tracking resistance, JP-A-3-13-1
No. 7,150, JP-A-6-57108, JP-A-7-145304, and the like. However, although any resin composition is a useful flame-retardant resin material for improving the tracking resistance, the flame-retardant amount is maintained along with the amount of the polyethylene resin or ethylene copolymer to maintain the flame retardancy. Also had the problem of increasing the amount.

[0011]

That is, the present invention relates to a flame-retardant reinforced polybutylene terephthalate resin composition which uses a non-halogen flame retardant and is excellent in mechanical properties, impact resistance, tracking resistance and flame retardancy. It is an object to obtain a molded product.

[0012]

Means for Solving the Problems In view of the above situation, the present inventors have made intensive studies and as a result, blended a specific amount of polyethylene terephthalate resin, red phosphorus and polyethylene and / or ethylene copolymer with PBT. It has been found that a flame-retardant reinforced polybutylene terephthalate resin composition and a molded article with specifically improved impact resistance and tracking resistance can be obtained while retaining highly excellent flame retardancy and mechanical properties by that, The present invention has been reached.

That is, the present invention relates to (A) 100 parts by weight of polybutylene terephthalate resin, (B) 1 to 200 parts by weight of polyethylene terephthalate resin, (C) 0.1 to 50 parts by weight of red phosphorus, (D) polyethylene and / Or ethylene copolymer 1
To 100 parts by weight (E) 0 to 100 parts by weight of a salt composed of a triazine compound and cyanuric acid or isocyanuric acid (F) 1 to 200 parts by weight of a fibrous reinforcing material (G) 0 to 30 parts by weight of an inorganic layered compound (H ) 0 to 10 parts by weight of a fluororesin (I) 0 to 30 parts by weight of a lubricant (J) 0 to 50 parts by weight of a carbon black (K) 0 to 10 parts by weight of a hindered phenol stabilizer and / or a phosphite stabilizer It is intended to provide a flame-retardant reinforced polybutylene terephthalate resin composition and a molded article containing the same.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant reinforced polybutylene terephthalate resin composition and the molded article of the present invention will be specifically described below.

The polybutylene terephthalate resin (A) of the present invention is a polymer obtained by a polycondensation reaction containing terephthalic acid or its ester-forming derivative and 1,4-butanediol or its ester-forming derivative as main components. Alternatively, it is a copolymer. Preferred examples of these polymers or copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate),
Examples thereof include polybutylene (terephthalate / decanedicarboxylate) and polybutylene (terephthalate / naphthalate), which may be used alone or as a mixture of two or more. Here, “/” means copolymerization.

The copolymerization amount of the above copolymer is not particularly limited as long as the properties of polybutylene terephthalate are not significantly impaired, but is about 0 to 30 mol% based on the total number of moles of the terephthalic acid component. It is preferably, more preferably about 0 to 25 mol%, and still more preferably about 0 to 20 mol%.

The polymer or copolymer has an intrinsic viscosity of 0.36 to 1.60, particularly 0.52 to 1.25, measured at 25 ° C. using an O-chlorophenol solvent. Are preferred in terms of mechanical properties and moldability.

Further, the polybutylene terephthalate polymer or copolymer has a COOH terminal group content of 1 to 3, which is determined by potentiometric titration of an m-cresol solution with an alkaline solution.
Those having a range of 50 eq / t (terminal group amount per ton of polymer) can be preferably used from the viewpoint of durability and anisotropy suppressing effect.

The (B) polyethylene terephthalate resin of the present invention refers to a high molecular weight thermoplastic polyester resin having an ester bond in the main chain, using terephthalic acid as an acid component and ethylene glycol as a glycol component.
In addition, as an acid component, isophthalic acid, adipic acid, oxalic acid, etc., as a glycol component, as a glycol component, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6 -Hexanediol, decamethylene glycol, cyclohexane dimethanol, cyclohexanediol, or the like, or a long-chain glycol having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,
20% by mole or less of 3-propylene glycol, polytetramethylene glycol, or the like can be used. Also,
The polyethylene terephthalate resin (B) having an intrinsic viscosity of 0.36 to 1.60, particularly 0.45 to 1.15 measured at 25 ° C. using an O-chlorophenol solvent has mechanical properties and molding properties. It is preferable from the viewpoint of sex. The amount of the (B) polyethylene terephthalate resin is from 1 to 200 parts by weight, preferably from 2 to 190 parts by weight, per 100 parts by weight of the (A) polybutylene terephthalate resin.
If the amount is too small, the flame retardancy is impaired. If the amount is too large, the tracking resistance is impaired.

The red phosphorus (C) used in the present invention is unstable as it is, and has a property of gradually dissolving in water. Can be As a method for treating such red phosphorus, without crushing red phosphorus described in JP-A-5-229806, without forming a crushed surface having high reactivity with water or oxygen on the surface of red phosphorus, A method of finely dividing red phosphorus, a method of catalytically suppressing the oxidation of red phosphorus by adding a small amount of aluminum hydroxide or magnesium hydroxide to red phosphorus, a method of coating red phosphorus with paraffin or wax to prevent contact with moisture. A method of suppressing, a method of stabilizing by mixing with ε-caprolactam or trioxane, and a method of stabilizing red phosphorus by coating it with a thermosetting resin such as a phenolic, melamine, epoxy, or unsaturated polyester resin. Red phosphorus is treated with an aqueous solution of a metal salt such as copper, nickel, silver, iron, aluminum and titanium to precipitate a metal phosphorus compound on the red phosphorus surface and to stabilize the red phosphorus. Stable by coating red phosphorus with aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide, etc., and electroless plating coating red phosphorus surface with iron, cobalt, nickel, manganese, tin, etc. And a method in which these are combined. Preferably, a method in which red phosphorus is stabilized by coating with a thermosetting resin such as a phenol-based, melamine-based, epoxy-based, and unsaturated polyester-based resin, or a method in which red phosphorus is used. This is a method in which phosphorus is stabilized by coating it with aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide, or the like. In addition, the average particle size of red phosphorus before being blended with the resin, the flame retardancy of the molded product,
From the viewpoint of mechanical strength and surface appearance, those having a thickness of 50 to 0.01 μm are preferable, and more preferably 45 to 0.1 μm.
belongs to. The average particle size of red phosphorus can be measured by a general laser diffraction type particle size distribution analyzer. The particle size distribution measuring apparatus includes a wet method and a dry method, and any of them may be used. In the case of the wet method, water can be used as a dispersion solvent for red phosphorus. At this time, red phosphorus surface treatment may be performed with an alcohol or a neutral detergent. It is also possible to use phosphates such as sodium hexametaphosphate and sodium pyrophosphate as the dispersant. It is also possible to use an ultrasonic bath as a dispersing device.

The conductivity of the (C) red phosphorus used in the present invention when extracted in hot water (where the conductivity is determined by adding 100 mL of pure water to 5 g of red phosphorus,
Extraction treatment at 21 ° C. for 100 hours, the filtrate after red phosphorus filtration can be diluted to 250 mL and measured), usually from 0.1 to 1 in view of flame retardancy and mechanical strength of the obtained molded article.
000 μS / cm, preferably 0.1 to 800 μ
S / cm, more preferably 0.1 to 500 μS / cm
It is.

Further, (C) the amount of phosphine generated by red phosphorus (C) used in the present invention (here, the amount of phosphine generated is set to 10 mmHg by placing 5 g of red phosphorus in a container having a capacity of 500 mL, for example, a test tube, etc. After decompression, 1 at 280 ° C
After heating for 0 minutes, cooling to 25 ° C., diluting the gas in the test tube with nitrogen gas to return to 760 mmHg, measuring using a phosphine (hydrogen phosphide) detector tube, and obtaining by the following formula. The amount of phosphine generated (ppm) = indicated value of detector tube (ppm) x dilution ratio) is the amount of gas generated from the composition, stability during extrusion and molding, mechanical strength during melt retention, surface appearance of molded product From the viewpoint of terminal corrosion due to a molded product, the content is usually 100 ppm or less, preferably 50 ppm or less, more preferably 20 ppm or less.

Commercially available red phosphorus exhibiting such preferred red phosphorus particles, conductivity and phosphine generation amount include "NOVA EXCEL 140" and "NOVA EXCEL F" manufactured by Rin Kagaku Kogyo.
5 "and the like.

In the present invention, the amount of (C) red phosphorus added is
0.1 to 50 parts by weight, preferably 0.1 to 45 parts by weight, based on 100 parts by weight of the polybutylene terephthalate resin,
More preferably, it is 0.2 to 40 parts by weight, and still more preferably 0.3 to 35 parts by weight.

Further, by adding a metal oxide as a stabilizer for red phosphorus, stability and strength during extrusion and molding can be improved.
Heat resistance and the like can be improved. Specific examples of such a metal oxide include cadmium oxide, zinc oxide,
Cuprous oxide, cupric oxide, ferrous oxide, ferric oxide, cobalt oxide, manganese oxide, molybdenum oxide, tin oxide, titanium oxide and the like, among which cadmium oxide, cuprous oxide, Cupric oxide and titanium oxide are preferred, and cuprous oxide, cupric oxide and titanium oxide are particularly preferred. Among them, titanium oxide is preferable.

The amount of the metal oxide to be added is preferably 0.01 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight, per 100 parts by weight of the polybutylene terephthalate resin (A) from the viewpoint of mechanical properties and moldability. Department.

The polyethylene in the polyethylene (D) and / or the ethylene copolymer used in the present invention includes high-density polyethylene, low-density polyethylene and ultra-low-density polyethylene, and the above-mentioned polyethylenes include acid anhydrides such as maleic anhydride. And / or polyethylene graft-polymerized with glycidyl methacrylate. One or more selected from these are used.

Examples of the ethylene copolymer include copolymers containing usually 50 mol% or more, preferably 70 mol% or more of ethylene. Monomers copolymerizable with ethylene include propylene, butene-1, vinyl acetate, isoprene, butadiene, monocarboxylic acids such as acrylic acid and methacrylic acid, and dicarboxylic acids such as ester acids, maleic acid, fumaric acid, and itaconic acid. And acid anhydrides such as maleic anhydride and glycidyl methacrylate. These can be used alone or in combination of two or more, and can be obtained as an ethylene copolymer by copolymerization by a usual method. Further, as in the case of polyethylene, a copolymer obtained by graft-polymerizing an acid anhydride such as maleic anhydride and / or glycidyl methacrylate onto the above-mentioned ethylene copolymer may also be used. One or more of these ethylene copolymers are used.

(D) Among polyethylene and / or ethylene copolymers, preferred are polyethylene and / or ethylene copolymers obtained by graft-polymerizing or copolymerizing acid anhydrides and glycidyl methacrylate. Alternatively, a copolymer obtained by graft polymerization or copolymerization of glycidyl methacrylate has good compatibility with PBT and is preferably used.
The amount of grafting or copolymerization of the above acid anhydride or glycidyl methacrylate is preferably 0.01 to 10% by weight, more preferably 0.01 to 5% by weight.

The amount of (D) polyethylene and / or ethylene copolymer is preferably from 1 to 100 parts by weight, particularly preferably from 1 to 90 parts by weight, per 100 parts by weight of (A) polybutylene terephthalate resin. If too small, the effect of improving impact resistance and tracking resistance is small,
If the amount is too large, the flame retardancy decreases, which is not preferable.

The (E) triazine compound and a salt of cyanuric acid or isocyanuric acid used in the present invention are:
It is an adduct of cyanuric acid or isocyanuric acid and a triazine-based compound, and is usually an adduct having a composition of 1: 1 (molar ratio), and sometimes 1: 2 (molar ratio).
Of the triazine compounds, those that do not form a salt with cyanuric acid or isocyanuric acid are excluded.

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

[0033]

Embedded image In the general formula (1), R ¹ , R ² , R ³ , and R ⁴ are the same or different, hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, or —CONH ₂ .
Here, the aryl group has 6 to 15 carbon atoms, the alkyl group has 1 to 10 carbon atoms, the aralkyl group has 7 to 16 carbon atoms, and the cycloalkyl group has 4 to 15 carbon atoms. Is preferred. Further, -NR ₁ R ₂ or -NR ³ R ⁴ the same groups for R in the above formula, or their and independently hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, -NH ₂ or -CONH, ₂ , wherein the aryl group has 6 to 15 carbon atoms, the alkyl group has 1 to 10 carbon atoms, the aralkyl group has 7 to 16 carbon atoms, and the cycloalkyl group Preferably have 4 to 15 carbon atoms.

Specific examples of R ¹ , R ² , R ³ and R ⁴ include hydrogen, phenyl, p-toluyl, α-naphthyl,
β-naphthyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, hydroxymethyl group, methoxymethyl group, benzyl group, cyclopentyl group, cyclohexyl group , A cycloheptyl group, a 2-methyl-1-pentyl group, a 4-methyl-1-cyclohexyl group, an amide group and the like, among which hydrogen, a phenyl group, a methyl group, a hydroxymethyl group, a methoxymethyl group, a benzyl group And an amide group is preferred.

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

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

The salt (E) of the triazine compound and cyanuric acid or isocyanuric acid is prepared by mixing a mixture of the triazine compound and cyanuric acid or isocyanuric acid with a water slurry, and mixing the two to form fine particles. It is a powder obtained by filtering and drying this slurry after forming into a shape, and is different from a mere mixture. This salt does not need to be completely pure, and may contain some unreacted triazine compound or cyanuric acid or isocyanuric acid. (A) The average of the salt before being mixed with the polybutylene terephthalate resin. The particle size is preferably from 100 to 0.01 μm, more preferably from 80 to 10 μm, in view of the flame retardancy, mechanical strength and surface properties of the molded article. If the salt has poor dispersibility, a dispersant such as tris (β-hydroxyethyl) isocyanurate may be used in combination. Further, (E) the amount of the salt of the triazine-based compound and cyanuric acid or isocyanuric acid added is (A)
The amount is usually 0 to 100 parts by weight, preferably 1 to 100 parts by weight, more preferably 1 to 95 parts by weight, and still more preferably 1 to 90 parts by weight based on 100 parts by weight of the polybutylene terephthalate resin.

As the fibrous reinforcing material (F) of the present invention, glass fiber, aramid fiber and the like can be mentioned. Examples of the above glass fibers include chopped strand type and roving type glass fibers used for a normal PBT reinforcing material, and a silane coupling agent such as an aminosilane compound or an epoxysilane compound and / or bisphenol A glycidyl ether or the like. Glass fibers treated with a sizing agent containing at least one epoxy compound such as a novolak epoxy compound are preferably used.

The amount of the fibrous reinforcing material (F) is 1 to 100 parts by weight of the polybutylene terephthalate resin (A).
To 200 parts by weight, particularly preferably 1 to 190 parts by weight.
If the amount is too small, the mechanical properties are deteriorated. If the amount is too large, the impact resistance and the appearance of the molded product are unfavorably deteriorated.

The (G) inorganic layered compound of the present invention is an inorganic compound in which unit crystal layers are stacked on each other, have a layered crystal structure, and have cleavage. Specific examples of the inorganic layered compound include kaolinite, talc, smectite, vermiculite, silicates such as mica, and phosphates such as zirconium phosphate and titanium phosphate.These inorganic layered compounds are treated with a coupling agent. Alternatively, an organic treatment for ion-exchanging inorganic ions between layers with organic ions may be performed. (G) The amount of the inorganic layered compound added is (A) polybutylene terephthalate 10
0 to 30 parts by weight per 0 parts by weight, preferably 0 to 30 parts by weight
It is 25 parts by weight, and if it is too much, mechanical properties tend to be impaired. Further, in order to improve the appearance of the molded article, it is preferable to add 0.02 parts by weight or more of an inorganic layered compound.
Further, the average particle size of the inorganic layered compound is preferably 0.1 to 4 μm, particularly preferably 0.3 to 3 μm from the viewpoint of mechanical properties.

The (H) fluorine-based resin of the present invention is a fluorine-based resin exhibiting an effect of suppressing the drop (drip) of droplets during combustion. Examples of such a fluororesin include polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, and (tetrafluoroethylene /
(Perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / ethylene) copolymer, and the like. Is, among others, polytetrafluoroethylene, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer,
Polyvinylidene fluoride is preferred, and polytetrafluoroethylene and (tetrafluoroethylene / ethylene) copolymer are particularly preferred. The amount of the (H) fluorine-based resin is usually from 0 to 1 based on 100 parts by weight of the (A) polybutylene terephthalate resin in view of mechanical properties and moldability.
0 parts by weight, preferably 0 to 8 parts by weight, more preferably 0 to 6 parts by weight, and if too much, the impact resistance tends to be impaired. In order to exhibit the effect of suppressing drip, it is preferable to add 0.02 parts by weight or more of a fluororesin.

The lubricant (I) of the present invention is a lubricant for plastics, and includes metal soaps such as calcium stearate and barium stearate, fatty acid esters, and salts of fatty acid esters (including those partially salted), Fatty acid amides such as ethylenebisstearamide, polycondensates of ethylenediamine and stearic acid and sebacic acid or fatty acid amides of polycondensates of phenylenediamine with stearic acid and sebacic acid, polyalkylene waxes, acid anhydride-modified polyalkylenes Examples include, but are not limited to, wax. Also, (I)
The amount of the lubricant to be added is (A) polybutylene terephthalate 1
0 to 30 parts by weight, preferably 0 to 100 parts by weight.
If it is too much, mechanical properties tend to be impaired. In order to improve the appearance of the molded product, 0.02
It is preferable to add a lubricant in an amount of at least part by weight.

The carbon black (J) of the present invention is a pigment which can be generally blended with plastics, and the amount of carbon black is 0 to 20 parts by weight based on 100 parts by weight of the polybutylene terephthalate resin (A). , Preferably 0 to 18 parts by weight, more preferably 0 to 15 parts by weight. If the amount is too large, mechanical properties tend to be impaired. Also,
In order to color black, it is preferable to add 0.05 parts by weight or more of carbon black.

The hindered phenol-based stabilizer and / or phosphite-based stabilizer (K) of the present invention is an additive which exhibits an extremely good effect on heat aging even when exposed to a high temperature for a long time. Examples of such a hindered phenol-based stabilizer include triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] and 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-hydrocinnamide), N, N'-trimethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide) and the like. Examples of the phosphite-based stabilizer include tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl osfite, Trisnonylphenyl phosphite, alkyl allyl phosphite, trialkyl phosphite, triallyl phosphite, pentaerythritol phosphite compound and the like can be mentioned.

In the present invention, such a hindered phenol-based stabilizer and / or phosphite-based stabilizer (K) can be added as needed. 0 to 10 parts by weight, preferably 0.01 to 8 parts by weight, more preferably 0.02 parts by weight, based on 100 parts by weight of the polybutylene terephthalate resin (A).
If it is too much, mechanical properties tend to be impaired. Further, in order to sufficiently obtain the effect of improving the heat aging resistance, it is preferable to add 0.01 parts by weight or more.

Further, the flame-retardant polybutylene terephthalate resin composition of the present invention does not impair the object of the present invention, such as sulfur-based and amine-based antioxidants, heat stabilizers, ultraviolet absorbers, mold release agents. One or more ordinary additives such as a coloring agent including a dye and a pigment can be added.

The flame-retardant polybutylene terephthalate resin composition of the present invention is produced by a generally known method. For example,
(A) polybutylene terephthalate resin, (B) polyethylene terephthalate resin, (C) red phosphorus, (D) polyolefin resin, (E) a salt comprising a triazine compound and cyanuric acid or isocyanuric acid, and other necessary (F) ) Premixing additives such as fiber reinforcement,
Alternatively, it is prepared by supplying the mixture to an extruder or the like without preliminary mixing and sufficiently kneading the mixture. However, from the viewpoint of handling properties and productivity, (A) a part of the polybutylene terephthalate resin, and / or (B) A part of polyethylene terephthalate resin and (C) red phosphorus are once melt-kneaded to produce a resin composition having a high red phosphorus concentration, and the remaining (A) polybutylene terephthalate resin or (B)
It is prepared by melt-kneading a polyethylene terephthalate resin with the resin composition having a high red phosphorus concentration and other optional additives. The above-mentioned red phosphorus having a high red phosphorus concentration is preferably used in the form of a so-called master pellet, but is not limited thereto, and may be in the form of a chip, a powder, or a mixture thereof. Further, the polybutylene terephthalate resin and the polyethylene terephthalate resin to be compounded at the time of the production of the master pellet are preferably in the form of pellets, but not limited thereto, so-called chips, powders, or a mixture of chips and powders. Is also good. Further, it is preferable that the polybutylene terephthalate resin and the polyethylene terephthalate resin to be blended with the master pellet have substantially the same shape, size, and shape, or that they are similar to each other, since they can be uniformly mixed. Also,
When adjusting the red phosphorus having a high red phosphorus concentration, (D)
A part or the whole of a salt composed of polyethylene and / or eccentric copolymer or (E) a triazine compound and cyanuric acid or isocyanuric acid may be used in combination. Further, (F) the method of adding the fiber reinforcing material by installing a side feeder in the middle of the base portion and the vent portion of a multi-screw extruder such as a twin-screw extruder may be used.

In producing the resin composition, for example, but not limited to, a single-screw extruder, a twin-screw extruder, a three-screw extruder, and a kneader of a kneader type equipped with a “unimelt” type screw Machine or the like can be used.

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, compression molding, etc., and molded articles such as sheets and films. Above all, it is particularly suitable for use in injection molded articles, and can be usefully used as electrical and electronic parts such as mechanical mechanism parts, connectors, and automobile parts by utilizing its features. Further, the present invention can be suitably used for an insert molding technique for directly molding a molding material on a part of a metal part.

[0050]

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 Tensile yield strength of a dumbbell test piece injection-molded using a Toshiba Machine's IS55EPN injection molding machine at a molding temperature of 270 ° C. and a mold temperature of 80 ° C. is measured in accordance with ASTM D-638. It was measured.

(2) Impact resistance Using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd., injection molding was performed at a molding temperature of 270 ° C. and a mold temperature of 80 ° C.
ASTM D for Izod impact test specimens
According to -256, Izod impact strength was measured.

(3) Flame Retardancy Flame retardancy evaluation test pieces injection molded using a Toshiba Machine's IS55EPN injection molding machine at a molding temperature of 270.degree. C. and a mold temperature of 80.degree. The flame retardancy was evaluated according to the evaluation criteria. Flame retardant level is V-0
>V-1>V-2> HB. The thickness of the test piece is 1/32 "and 1/64", and the smaller the thickness, the severer the flame retardancy.

(4) Tracking Resistance Using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd., injection molding was performed at a molding temperature of 270 ° C. and a mold temperature of 80 ° C.
A square plate of 0 mm x 80 mm x 3 mm thickness was used as a sample, and the IE
The relative tracking index (CTI value) was determined according to the test method specified in the C Publication 112 standard. The higher the applied voltage at the time of the test, the better the CTI value,
It is measured at an applied voltage in the range of 0V to 600V.

(5) Appearance With respect to the dumbbell test piece obtained in the above (1), the appearance of the molded article was visually observed, and the appearance was judged according to the following criteria.

◎: The entire molded article is glossy ○: A part of the molded article has no gloss Δ: About half of the molded article is not glossy ×: The entire molded article is not glossy 25, Comparative Examples 1 to 11 Using a twin-screw extruder (TEX-30α, manufactured by Nippon Steel Works) with a screw diameter of 30 mm and L / D35 having the same direction of rotation, (A) an intrinsic viscosity of 0.85 (25 ° C.) , An o-chlorophenol solution) of 100 parts by weight of a polybutylene terephthalate resin (hereinafter abbreviated as PBT), and (B) a polyethylene terephthalate resin (B) having an intrinsic viscosity of 0.65 (25 ° C., o-chlorophenol solution). PET) (abbreviated as PET), (C) Red phosphorus (“NOVA EXCEL F5” manufactured by Rin Kagaku Kogyo Co., Ltd.) and other additives were mixed in the ratios shown in Tables 1 to 3 and added from the filling portion. Further, a side feeder was installed in the middle of the filling section and the vent section, and (F) glass fiber ("CS3PE941S" manufactured by Nitto Boseki Co., Ltd.) was added in the same amount as shown in Tables 1 and 2 as described above. The kneading temperature 2
The mixture was melt-mixed under extrusion conditions of 80 ° C. and a screw rotation of 150 rpm, discharged in a strand shape, passed through a cooling path, and pelletized by a strand cutter. Further, after drying the obtained pellets, ASTM D-6 is obtained by injection molding.
ASTM D-256, tensile test specimen specified in 38
Izod impact test specimen specified in 3mm8
A 0 mm square plate and a test piece for evaluating flame retardancy based on UL94 were prepared.

The measurement results of the mechanical properties, impact strength, tracking resistance and flame retardancy of each sample are shown in Tables 1 and 2 in the same manner as in the above formulation.

Further, other additives of the present invention are shown below.

(D) Polyethylene and / or ethylene copolymer D-1 Low density polyethylene ("Mirason" 50 manufactured by Mitsui Petrochemical Industries) D-2 Polypropylene ("Mitsui Noblen" JS-G manufactured by Mitsui Toatsu Chemicals) D -3 Ethylene / glycidyl methacrylate copolymer ("Bond First-E" manufactured by Sumitomo Chemical) D-4 Ethylene / butene-1 / maleic anhydride copolymer ("MH5020" manufactured by DuPont Mitsui Polychemicals) D-5 ethylene / Ethyl acrylate copolymer (“Evaflex-EEA” A manufactured by Mitsui Dupont Polychemicals)
-701) (E) Cyanurate, melamine cyanurate (“MC440” manufactured by Nissan Chemical Industries, Ltd.) (G) Inorganic layered compound (Talc “HE- manufactured by Takehara Chemical Co., Ltd.)
5 ") (H) Fluorine-based resin, polytetrafluoroethylene (" Teflon 6J "manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd.) (I) Lubricant I-1. Lubricant in which a part of fatty acid ester was converted to salt (" Hoechst "manufactured by Hoechst Japan) Wax OP ") I-2. Polycondensate composed of ethylenediamine, stearic acid and sebacic acid (Kyoeisha Chemical" Light Amide WH-255 ") I-3. Acid anhydride-modified polyalkylene wax (Mitsui Petrochemical Industries" (J) Carbon black (Mitsubishi Chemical # 3050) (K) K-1. Hindered phenol-based stabilizer, pentaerythryl-tetrakis [3- (3,5-di-t-butyl) -4-Hydroxyphenyl) propionate] (“IR-1010” manufactured by Ciba-Geigy) K-2.Phosphite stabilizer, pentaerythritol Phosphite compound (Asahi Denka Ltd. "PEP-24G") halogen-based flame retardant brominated polycarbonate (produced by Teijin Chemicals Ltd. "FG7500") antimony trioxide (Nihonseiko Ltd. "PAT0X-M")

[0060]

[Table 1]

[0061]

[Table 2]

From the evaluation results of Examples 1 to 15 in Table 1, PB
T is blended with a specific amount of PET, red phosphorus, polyethylene and / or ethylene copolymer, glass fiber, or a triazine-based compound of the present invention to provide excellent mechanical properties, impact resistance, and excellent tracking resistance. It is evident that it exhibits properties and flame retardancy.

From Comparative Examples 1 to 4, it is clear that when any one component of the composition of the present invention is not added, excellent tracking resistance and flame retardancy cannot be exhibited. . Further, in the composition of Comparative Example 5 in which the PET amount exceeds 200 parts by weight, the impact resistance is reduced, and the material adheres to the mold during injection molding, and is released within a predetermined molding time. Was not obtained, and the injection moldability was poor.
Further, from Comparative Example 6, the use of an olefin resin made of polypropylene is not preferable because the mechanical properties and impact resistance are greatly impaired. On the other hand, if the amount of polyethylene and / or ethylene copolymer in Comparative Example 7 exceeds 100 parts by weight, the mechanical properties and flame retardancy are undesirably reduced. On the other hand, when the amount of the cyanuric acid salt in Comparative Example 8 exceeds 100 parts by weight, the mechanical properties and the impact resistance are undesirably reduced. Comparative Example 9 is a composition using a halogen-based flame retardant obtained by using 42 parts by weight of brominated polycarbonate and 13 parts by weight of antimony trioxide in place of the composition shown in Table 1 and further replacing red phosphorus or cyanurate. It is clear that the flame retardancy is excellent but the tracking resistance is inferior. Further, in Comparative Example 10, when the amount of polyethylene and / or ethylene copolymer was increased in the material of Comparative Example 9 to improve the tracking resistance in order to improve the tracking resistance, it was found that the flame retardancy was greatly impaired. became.

From the evaluation results of Examples 16 to 25 in Table 2, when one of talc and a lubricant is added to the composition of the present invention or a combination thereof, the mechanical properties, impact resistance, tracking resistance and flame retardancy are maintained. However, an effect was observed in improving the appearance of the molded product. On the other hand, when the glass fiber content of Comparative Example 11 exceeds 200 parts by weight, the impact resistance is lowered and the appearance of the molded product is deteriorated, and the commercial value is undesirably reduced. Further, it can be seen that further improved flame retardancy can be obtained by blending any one of or a combination of the fluorine resin and the stabilizer with the composition of the present invention. It can also be seen that the excellent properties of the present invention are maintained even when a carbon black pigment is blended with the composition of the present invention.

[0065]

By mixing PET, red phosphorus, polyethylene and / or an ethylene copolymer and a fibrous reinforcing material with PBT, it is excellent in mechanical properties, impact resistance, trackability and flame retardancy. A flame-retardant reinforced polybutylene terephthalate resin composition using a non-halogen-based flame retardant having both of the following characteristics is obtained, and the flame-retardant reinforced polybutylene terephthalate resin composition is suitable for electric parts such as automobile parts, connectors, and mechanical parts. And a molded article including an insert molded article.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/13 C08K 5/13 5/3492 5/3492 5/524 5/524 7/02 7/02 7/14 7/14 9/04 9/04 9/08 9/08 C08L 23/04 C08L 23/04 51/06 51/06 // C08J 5/08 C08J 5/08 5/10 CFD 5/10 CFD (C08L 67/02 23 : 04 27:12) (72) Inventor Koji Yamauchi 1 Toray Co., Ltd. Nagoya Office, 9-9 Oe-cho, Minato-ku, Nagoya-shi, Aichi

Claims (7)

[Claims] 1. A polybutylene terephthalate resin (A)
(B) 1 to 200 parts by weight of polyethylene terephthalate resin (C) 0.1 to 50 parts by weight of red phosphorus (D) polyethylene and / or ethylene copolymer 1
To 100 parts by weight (E) 0 to 100 parts by weight of a salt composed of a triazine compound and cyanuric acid or isocyanuric acid (F) 1 to 200 parts by weight of a fibrous reinforcing material (G) 0 to 30 parts by weight of an inorganic layered compound (H ) 0 to 10 parts by weight of a fluororesin (I) 0 to 30 parts by weight of a lubricant (J) 0 to 30 parts by weight of a carbon black (K) 0 to 10 parts by weight of a hindered phenol stabilizer and / or a phosphite stabilizer And a flame-retardant reinforced polybutylene terephthalate resin composition. 2. The flame-retardant reinforced polybutylene terephthalate resin composition according to claim 1, wherein (C) red phosphorus is red phosphorus coated with a thermosetting resin. 3. The polyethylene and / or ethylene copolymer (D) contains a polyethylene and / or ethylene copolymer obtained by graft-polymerizing or copolymerizing an acid anhydride and glycidyl methacrylate. The flame-retardant reinforced polybutylene terephthalate resin composition according to any one of the above. 4. The flame-retardant reinforced polybutylene terephthalate resin composition according to claim 1, wherein (F) the fibrous reinforcing material is glass fiber. 5. The flame-retardant material according to claim 1, wherein (F) a sizing agent mainly composed of a silane coupling agent and an epoxy compound is adhered to the surface of the glass fiber of the fibrous reinforcing material. A reinforced polybutylene terephthalate resin composition. 6. A molded article comprising the flame-retardant reinforced polybutylene terephthalate resin composition according to any one of claims 1 to 5, or a molded article in which a metal is inserted. 7. The molded article according to claim 6, wherein the flame-retardant reinforced polybutylene terephthalate molded article is a mechanical mechanism part, an electric / electronic part or an automobile part.