JPH11335533A - Resin composition for coil bobbin made from flame-retardant reinforced polybutylene terephthalate and coil bobbin made therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition for coil bobbins made from a flame- retardant reinforced PBT, having a high dielectric breakdown voltage and excellent heat resistance, tracking resistance, and impact strength and containing a nonhalogen flame retardant and to obtain a coil bobbin made therefrom. SOLUTION: Provided is a resin composition for coil bobbins made from a flame-retardant reinforced PBT (polybutylene terephthalate), 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) 0-100 pts.wt. salt of a triazine compound with cyanuric acid or isocyanuric acid, (F) 1-100 pts.wt. polyethylene and/or ethylene copolymer, (G) 0-30 pts.wt. inorganic layered compound, (H) 0-10 pts.wt. fluoro resin, (I) 0-30 pts.wt. lubricant, (J) 0-30 pts.wt. carbon black, and (K) 0-10 pts.wt. hindered phenol stabilizer and/or phosphite stabilizer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for a coil bobbin made of a polybutylene terephthalate having enhanced flame retardancy using a non-halogen flame retardant, and a coil bobbin comprising the same. More specifically, breakdown voltage, heat resistance,
The present invention relates to a coil bobbin resin composition having excellent tracking resistance, impact strength, and flame retardancy, and a coil bobbin comprising the same.

[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 and electronic parts, and automobile parts by making use of 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.

[0004] Since PBT is inherently flammable, especially for use as electrical and electronic parts, PBT has a safety against flame, that is, a balance between physical properties such as general chemical, heat resistance and impact strength. Often flame retardancy is required. In parts such as coil bobbins, the more easily carbonized resin is subjected to electric energy when it is applied to the resin, the easier it is to conduct electricity, and resistance heat is also added, an arc tracking route is generated, and finally the resin ignites and burns. There is a possibility of progress, and a material having the above-described flame retardancy, tracking resistance, and dielectric strength is required.

[0005] 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, the addition of 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 resin composition is a useful flame-retardant resin material that does not use a halogen-based flame retardant, these coil bobbins have a dielectric breakdown voltage,
Since any of heat resistance, tracking resistance, and impact strength is deteriorated, it has problems such as easy breakage, easy melting deformation during soldering, and the possibility of ignition during long-term use of the product. Was.

[0009]

That is, the present invention uses a non-halogen flame retardant and is made of flame-retardant reinforced polybutylene terephthalate which is excellent in dielectric breakdown voltage, heat resistance, tracking resistance, impact strength and flame retardancy. It is an object to obtain a coil bobbin.

[0010]

Means for Solving the Problems In view of the above situation, the present inventors have conducted intensive studies and as a result, have found that PBT is composed of a specific amount of polyethylene terephthalate resin, red phosphorus, fibrous reinforcing material and ethylene resin. The flame-retardant polybutylene terephthalate resin composition is highly useful as a coil bobbin because it has specifically improved insulation breakdown voltage, heat resistance, tracking resistance and impact strength while maintaining highly excellent flame retardancy. The present inventors have found that there is a coil bobbin made of polybutylene terephthalate with enhanced flame retardancy of the present invention.

That is, the present invention relates to (A) 100 parts by weight of a polybutylene terephthalate resin, (B) 1 to 200 parts by weight of a polyethylene terephthalate resin, (C) 0.1 to 50 parts by weight of red phosphorus, and (D) a triazine-based resin. 0-100 parts by weight of salt comprising compound and cyanuric acid or isocyanuric acid (E) 1-200 parts by weight of fibrous reinforcing material (F) Polyethylene and / or ethylene copolymer 1
To 100 parts by weight (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 carbon black (K) hindered An object of the present invention is to provide a resin composition for a coil bobbin made of flame-retardant reinforced polybutylene terephthalate, which contains 0 to 10 parts by weight of a phenol stabilizer and / or a phosphite stabilizer, and a coil bobbin comprising the same.

[0012]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The coil bobbin made of polybutylene terephthalate with enhanced flame retardancy 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 comprising terephthalic acid or an ester-forming derivative thereof and 1,4-butanediol or an ester-forming derivative thereof 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 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. Is preferred. If the intrinsic viscosity is too low, the impact strength tends to be impaired, but it is poor. If the intrinsic viscosity is too high, the moldability tends to be impaired.

Further, these polybutylene terephthalate polymers or copolymers have a COOH terminal group content of 1 to 3 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. If the amount of COOH terminal group is less than 1, the effect of suppressing anisotropy is not sufficient, and if the amount of COOH terminal group exceeds 50, durability becomes poor and both are not preferred.

The (B) polyethylene terephthalate resin of the present invention refers to a high molecular weight thermoplastic polyester resin having an ester bond in its 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,
As the polyethylene terephthalate resin (B), those 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 are suitable. If the intrinsic viscosity is too low, impact strength tends to be impaired, and if the intrinsic viscosity is too high, moldability tends to be impaired. The blending amount of (B) the polyethylene terephthalate resin is 1 to 200 parts by weight, preferably 2 to 190 parts by weight, based on 100 parts by weight of the (A) polybutylene terephthalate resin. If the amount is too large, the tracking resistance is impaired.

The (C) red phosphorus used in the present invention is unstable as it is, and has the 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. Further, the above stabilization methods may be used in combination. The average particle size of red phosphorus before being blended with the resin is preferably 50 to 0.01 μm, more preferably 45 to 0.1 μm, from the viewpoint of flame retardancy, impact strength and appearance of the molded product. 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.

The amount of phosphine generated by (C) red phosphorus used in the present invention (here, the amount of phosphine generated is determined by placing 5 g of red phosphorus in a container such as a test tube having a capacity of 500 mL and replacing with nitrogen by 10 mmHg. 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 preferred.

The addition amount of the metal oxide 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 triazine compound (D) and the 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).

[0026]

Embedded image In the above general formula (1), R ¹ , R ² , R ³ , R ⁴
Are the same or different hydrogen, aryl group, alkyl group,
An aralkyl group, a cycloalkyl group, or -CONH ₂
It is. 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. Also,
R is -NR ₁ R ₂ or -NR ³ R ⁴ the same group in the above formula or their independent hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, -NH
_2, or a group selected from -CONH _2, where the aryl groups those having from 6 to 15 carbon atoms, the alkyl group as having 1 to 10 carbon atoms, aralkyl group of 7 to 16 carbon atoms And cycloalkyl groups having 4 to 15 carbon atoms are preferred.

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

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

Among the salts of the compound represented by the general formula (1) with cyanuric acid or isocyanuric acid, melamine, benzoguanamine, acetoguanamine, 2-acetguanamine,
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.

Further, (D) a salt of a triazine compound and cyanuric acid or isocyanuric acid is prepared by mixing a mixture of the triazine compound and cyanuric acid or isocyanuric acid with a water slurry, and mixing them well to form fine particles of both salts. 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 100 to 0.01 μm from the viewpoint of flame retardancy, impact strength and appearance of the molded product,
More preferably, it is 80 to 10 μm. If the salt has poor dispersibility, a dispersant such as tris (β-hydroxyethyl) isocyanurate may be used in combination. The amount of the salt of (I) a triazine compound and cyanuric acid or isocyanuric acid is usually 0 to 100 parts by weight, preferably 1 to 100 parts by weight, per 100 parts by weight of (A) polybutylene terephthalate resin. Department,
More preferably 1 to 90 parts by weight, even more preferably 1 to 90 parts by weight
80 parts by weight.

Examples of the fibrous reinforcing material (E) of the present invention include glass fibers and aramid fibers. 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 (E) is preferably from 1 to 200 parts by weight, particularly preferably from 2 to 190 parts by weight, per 100 parts by weight of the polybutylene terephthalate resin (A). If the amount is too large, the impact strength is impaired.

The (F) polyethylene and / or polyethylene in 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 and acid anhydrides such as maleic anhydride. And / or polyethylene graft-polymerized with glycidyl methacrylate. One or more selected from these are used.

As the ethylene copolymer, a copolymer containing usually 50 mol% or more, preferably 70 mol% or more of ethylene is exemplified. 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 1 to 100 parts by weight, particularly preferably 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 (G) inorganic layered compound used in the present invention is an inorganic compound in which unit crystal layers are stacked on each other and have a layered crystal structure and have cleavage properties. 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. The amount of the inorganic layered compound (G) to be added is 0 to 30 parts by weight, preferably 0 to 25 parts by weight, per 100 parts by weight of the polybutylene terephthalate (A). If the amount is too large, the impact strength tends to be impaired. It is in. 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 impact strength and moldability.
The amount is 0 parts by weight, preferably 0 to 8 parts by weight, more preferably 0 to 6 parts by weight. If the amount is too large, mechanical properties tend 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.

[0038] 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, salts of fatty acid esters (including those in which salts are partially formed), 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 large, the impact strength tends 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 that can be generally incorporated into plastics. The amount of carbon black added 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, the impact strength tends 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. The amount is 0 to 10 parts by weight, preferably 0 to 8 parts by weight, more preferably 0 to 6 parts by weight, based on 100 parts by weight of the polybutylene terephthalate resin (A). If the amount is too large, the impact strength tends to be impaired. Further, in order to sufficiently obtain the effect of improving the heat aging resistance, the content of 0.1% is required.
It is preferable to add at least 01 parts by weight.

Furthermore, the resin composition for coil bobbins made of the flame-retardant reinforced polybutylene terephthalate of the present invention is not limited to the object of the present invention, as long as the object of the present invention is not impaired. Agent, release agent,
And ordinary additives such as coloring agents including dyes and pigments.
More than one species can be added.

The resin composition for coil bobbins made of flame-retardant reinforced polybutylene terephthalate 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) a salt composed of a triazine compound and cyanuric acid or isocyanuric acid, (E) a fiber reinforcing material and other necessary additives (F) such as polyethylene and / or an ethylene copolymer. The resin composition is prepared by preliminarily mixing or not being supplied to an extruder or the like and sufficiently melt-kneaded to prepare a resin composition. However, from the viewpoint of handling properties and productivity, it is preferable to use (A) a polybutylene terephthalate resin. A part 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, (F)
A part or all of a salt composed of polyethylene and / or an ethylene copolymer or (D) a triazine compound and cyanuric acid or isocyanuric acid may be used in combination. Further, (E) a method may be used in which the fiber reinforcing material is added 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.

In producing the resin composition, for example, but not limited to, a single-screw extruder, a twin-screw extruder, a tri-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 reinforced polybutylene terephthalate resin composition thus obtained can be usually molded by a known method, and for example, a coil bobbin can be obtained by injection molding, extrusion molding, compression molding or the like. Of these, injection molding is preferred.

[0046]

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) Heat Resistance (Heat Deformation Temperature) A dumbbell test piece injection-molded at a molding temperature of 270 ° C. and a mold temperature of 80 ° C. using an IS55EPN injection molding machine manufactured by Toshiba Machine in accordance with ASTM D-648. , Load 0.
The heat distortion temperature was measured under the condition of 45 MPa.

(2) Dielectric Breakdown Voltage 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 AS
The breakdown voltage was determined according to the test method specified in TM D149 standard.

(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 ° C. and a mold temperature of 80 ° C. are specified in UL94. 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 The injection molding was performed using a Toshiba Machine's IS55EPN injection molding machine 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 of Molded Article The dumbbell test piece obtained in the above (1) was visually observed for the appearance of the molded article, and the appearance was judged according to the following criteria.

◎: The entire molded article is glossy ○: There is a dull part in the molded article △: About half of the molded article is not glossy ×: The entire molded article is not glossy (6) Impact Strength Injection molding was performed using a Toshiba Machine's IS55EPN injection molding machine 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.

Examples 1 to 23 and Comparative Examples 1 to 10 Using a twin-screw extruder (TEX-30α, manufactured by Nippon Steel Works) having a screw diameter of 30 mm and L / D 35 with a co-rotating vent, (A) With respect to 100 parts by weight of a polybutylene terephthalate resin (hereinafter abbreviated as PBT) having an intrinsic viscosity of 0.65 (at 25 ° C, o-chlorophenol solution) at 0.85 (at 25 ° C, o-chlorophenol solution). ), (C) red phosphorus (“NOVA EXCEL F5” manufactured by Rin Kagaku Kogyo Co., Ltd.) and other additives at the ratios shown in Tables 1 to 3 and added from the mixing portion. did. Further, a side feeder was installed in the middle of the filling part and the vent part, and (E) glass fiber (“CS3J948” manufactured by Nitto Boseki Co., Ltd.) was added in the same amount as shown in Tables 1 and 2 as described above. In addition, kneading temperature 280
The mixture was melt-mixed under extrusion conditions of 150 ° C. and a screw rotation of 150 rpm, discharged in a strand form, passed through a cooling path, and pelletized by a strand cutter. Further, after drying the obtained pellet, ASTM D-638 by injection molding.
And a test piece for evaluating flame retardancy based on UL94 were prepared.

The heat distortion temperature, dielectric breakdown voltage,
The measurement results of flame retardancy, tracking resistance, impact strength, and appearance of the molded product are shown in Tables 1 and 2 in the same manner as the above formulation.

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

(D) Cyanurate, melamine cyanurate (“MC440” manufactured by Nissan Chemical Co., Ltd.) (F) Polyolefin resin F-1 Low density polyethylene (“Mirason” 50 manufactured by Mitsui Petrochemical Industries) F-2 Polypropylene (Mitsui F-3 Ethylene / glycidyl methacrylate copolymer (Sumitomo Chemical's "Bond First-E") F-4 Ethylene / butene-1 / maleic anhydride copolymer (Mitsui No. Blend JS-G) F-5 Ethylene / ethyl acrylate copolymer (“Evaflex-EEA” A-70 manufactured by DuPont Mitsui Polychemicals)
1) (G) Inorganic layered compound (Talc “HE-
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 -Based phosphite compound (“PEP-24G” manufactured by Asahi Denka) Halogen-based flame retardant Brominated polycarbonate (“FG7500” manufactured by Teijin Chemicals) Antimony trioxide (“PAT0X-M” manufactured by Nippon Seimitsu)

[0057]

[Table 1]

[0058]

[Table 2]

According to Examples 1 to 13 in Table 1, dielectric breakdown was caused by blending a specific amount of PET, red phosphorus, glass fiber, polyethylene and / or ethylene copolymer or a triazine compound of the present invention with PBT. Voltage,
It is evident that it has excellent heat resistance, tracking resistance and impact strength, and exhibits excellent flame retardancy.

Also, from Comparative Examples 1 to 10 in Table 1, one of the above-mentioned characteristics is excellent when any one component of the composition of the present invention is not added or when the compounding amount is out of the specified range. It is clear that it cannot exhibit any properties of either part or flame retardant, and is not a material that can be used as a coil bobbin. Further, from Comparative Example 9, when an olefin resin made of polypropylene was used, the impact strength was poor, and the material was not a material that could be used as a coil bobbin.

From Examples 14 to 17 and Example 23 in Table 2, when any one of talc and a lubricant is added to the composition of the present invention or a combination thereof, the appearance of the molded product is improved while maintaining the excellent characteristics of the present invention. The effect was recognized. Further, from Example 18 and Examples 20 to 23 in Table 2, it can be seen that further improved flame retardancy can be obtained by blending any one of or a combination of the fluororesin and the stabilizer with the composition of the present invention. .

Further, from Example 19 in Table 2, it can be seen that the excellent characteristics of the present invention are maintained even when a carbon black pigment is added to the composition of the present invention.

[0063]

By blending PET, red phosphorus, a fibrous reinforcing material and polyethylene and / or an ethylene copolymer with PBT, a non-halogen excellent in dielectric breakdown voltage, heat resistance, tracking resistance and impact strength is obtained. A flame-retardant reinforced polybutylene terephthalate resin composition for a coil bobbin using a system-based flame retardant and a coil bobbin are obtained,
It can be expected to greatly contribute to the expansion of the market for electrical and electronic components.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 9/08 C08K 9/08 C08L 23/04 C08L 23/04 27/12 27/12 H01F 5/02 H01F 5/02 M ( 72) Inventor Koji Yamauchi 1 Toray Co., Ltd. Nagoya Office, 9-9 Oecho, Minato-ku, Nagoya-shi, Aichi

Claims (6)

[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) 0 to 100 parts by weight of a salt comprising a triazine compound and cyanuric acid or isocyanuric acid Part (E) 1 to 200 parts by weight of fibrous reinforcing material (F) polyethylene and / or ethylene copolymer 1
To 100 parts by weight (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 carbon black (K) hindered A resin composition for a coil bobbin made of reinforced polybutylene terephthalate, comprising 0 to 10 parts by weight of a phenolic stabilizer and / or a phosphite stabilizer. 2. The resin composition for a coil bobbin made of flame-retardant reinforced polybutylene terephthalate according to claim 1, wherein (C) red phosphorus is red phosphorus coated with a thermosetting resin. 3. The method according to claim 1, wherein (F) the polyethylene and / or the ethylene copolymer contains a polyethylene and / or an ethylene copolymer obtained by copolymerizing at least one selected from maleic anhydride and glycidyl methacrylate. Or the resin composition for a coil bobbin made of flame-retardant reinforced polybutylene terephthalate according to 2 or 3. 4. The resin composition for a coil bobbin made of flame-retardant reinforced polybutylene terephthalate according to claim 1, wherein the fibrous reinforcing material is glass fiber. 5. The flame retardant according to claim 1, wherein (E) a sizing agent mainly composed of a silane coupling agent and an epoxy compound adheres to the surface of the glass fiber of the fibrous reinforcing material. A resin composition for a coil bobbin made of reinforced polybutylene terephthalate. 6. A coil bobbin made of a flame-retardant reinforced polybutylene terephthalate, comprising the resin composition for a coil bobbin made of a flame-retardant reinforced polybutylene terephthalate according to any one of claims 1 to 5.