JP2000178419A - Flame retardant polybutylene terephthalate resin composition for electrical part housing and electrical part housing comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame retardant polybutylene terephthalate resin composition for electrical part housings excellent in flame retardance, contact point fouling and tracking resistances, etc., and using a nonhalogen-based flame retardant. SOLUTION: This composition is obtained by compounding (A) 100 pts.wt. of a polybutylene terephthalate with (B) 1-200 pts.wt. of a polycarbonate and/or a polyethylene terephthalate, (C) 0.1-75 pts.wt. of a phenol resin and/or a phenoxy resin, (D) 0.1-50 pts.wt. of a red phosphorus, (E) 1-200 pts.wt. of a fibrous reinforcing material, (F) 0-100 pts.wt. of a polyolefin resin, (G) 0-30 pts.wt. of an inorganic layer compound, (H) 0-10 pts.wt. of a fluorine-based resin, (I) 0-10 pts.wt. of a silicone-based compound, (J) 0-30 pts.wt. of a lubricant, (K) 0-30 pts.wt. of carbon black and (L) 0-10 pts.wt. of a phenolic stabilizer and/or a phosphite-based 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 an electrical component housing made of a flame-retardant reinforced polybutylene terephthalate resin using a specific non-halogen flame retardant, and an electrical component housing comprising the same. More specifically, a resin composition and an electric contact switch which are excellent in contact contamination resistance, tracking resistance and flame retardancy, and which are suitable for a housing of an electric component having an electric contact switch such as an electric relay component or an electric switch component. The present invention relates to a housing of an electric component having:

[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. Further, by compounding a fiber reinforced material with PBT, it is widely used as a material having further excellent mechanical properties and heat resistance. Among the fiber reinforcements, glass fibers are particularly used. Because PBT is inherently flammable, it is particularly safe to use as an electrical or electronic component, in addition to the balance of general chemical properties and physical properties such as heat resistance and impact strength, as well as flame safety, Often flame retardancy is required. In addition, an electric component having an electric contact switching unit such as an electric relay component or an electric switch component is generally used by being incorporated in a home appliance or an OA device. When electric energy is applied to the electric component resin when using the equipment, the resin that is more likely to be carbonized will be easier to conduct electricity, and resistance heat will also be added, creating an arc tracking route,
At last, the resin ignites and proceeds to combustion, so that a material having the above-described flame retardancy and tracking resistance is required.
Further, there is a demand for a material having excellent contact contamination resistance which does not cause a contact failure of a relay or a switch portion due to a bleed-out component emitted from the material.

[0003] As a method of 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
Japanese Patent Application Laid-Open No. H3-320486 and Japanese Patent Application Laid-Open No. Hei 5-339417.

[0006]

However, although these resin compositions are all useful flame-retardant resin materials which do not use halogen-based flame retardants, they can be used to obtain electrical component housings such as relays and switches. When used as a product, there are problems such as the possibility of ignition during long-term use of the product or the inability to maintain sufficient product performance due to the deterioration of either the tracking resistance or the contact contamination resistance. Was.

Accordingly, the present invention provides a flame-retardant polybutylene terephthalate resin composition which uses a non-halogen flame retardant, is excellent in tracking resistance, contact contamination resistance and flame retardancy, and is suitable for use as an electrical component housing. An object of the present invention is to provide a housing of an electric component having an electric contact switching unit.

[0008]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, a specific amount of polycarbonate resin and / or polyethylene terephthalate resin, phenol resin and / or phenoxy resin was added to PBT. , A flame-retardant polybutylene terephthalate resin composition containing red phosphorus and a fibrous reinforcing material, while maintaining highly excellent flame retardancy, specifically improves tracking resistance and contact contamination resistance Therefore, the present invention has been found to be extremely useful as a housing for an electric component having an electric contact opening / closing portion such as a relay or a switch, and has accomplished the present invention.

That is, the present invention relates to (B) 1 to 200 parts by weight of a polycarbonate resin and / or a polyethylene terephthalate resin, and (C) a phenolic resin and / or a phenoxy resin with respect to 100 parts by weight of a polybutylene terephthalate resin. 0.1-75 parts by weight,
(D) 0.1 to 50 parts by weight of red phosphorus having a conductivity of 0.1 to 1000 μS / cm (provided that the conductivity is obtained by adding 100 mL of pure water to 5 g of red phosphorus and extracting at 121 ° C. for 100 hours;
The filtrate after filtering the red phosphorus is set to the conductivity of the extraction water diluted to 250 mL. ), (E) 1 to 200 parts by weight of a fibrous reinforcing material, (F) 0 to 100 parts by weight of at least one kind of polyolefin resin of polyethylene resin and polyolefin-based copolymer, (G) inorganic layered compound 0 To 30 parts by weight, (H) 0 to 10 parts by weight of a fluororesin, (I) 0 to 10 parts by weight of a silicone compound, (J) 0 to 30 parts by weight of a lubricant, (K) 0 to 30 parts by weight of carbon black, (L)
A flame-retardant polybutylene terephthalate resin composition for an electrical component housing, which comprises 0 to 10 parts by weight of a hindered phenol-based stabilizer and / or a phosphite-based stabilizer, and an electrical component having an electrical contact opening / closing portion comprising the same Is provided.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant polybutylene terephthalate resin composition for an electrical component housing of the present invention and the electrical component housing having an electrical contact opening / closing portion such as a relay or a switch made of the same are specifically described below. explain.

The polybutylene terephthalate resin (A) used in the present invention is obtained by a polycondensation reaction from a raw material containing terephthalic acid or its ester-forming derivative and 1,4-butanediol or its ester-forming derivative as main components. The resulting polymer or copolymer. Preferred examples of these polymers or copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decane dicarboxylate), and polybutylene. (Telephthalate /
Naphthalate) and the like, and may be used alone or as a mixture of two or more. Here, “/” means copolymerization.

[0012] The polymer or copolymer is an O-
Those having an intrinsic viscosity of 0.36 to 1.60, particularly 0.52 to 1.25, measured at 25 ° C. using a chlorophenol solvent are suitable. When the intrinsic viscosity is less than 0.36, the impact strength is poor, and when the intrinsic viscosity exceeds 1.60, the moldability becomes poor, and both are not preferred. Also,
(A) If the intrinsic viscosity of the polybutylene terephthalate resin is in the range of 0.36 to 1.60, two or more kinds of polybutylene terephthalate resins having different intrinsic viscosities may be used in combination.

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 polycarbonate resin used as the component (B) in the present invention is an aromatic homo- or copolycarbonate resin obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester. The molecular weight is 10,000 to 1,000,000
It should just be in the range of. Within the range of the viscosity average molecular weight, two or more kinds of polycarbonate resins having different viscosity average molecular weights may be used in combination.

Here, as the dihydric phenol compound,
2,2-bis (4-hydroxyphenyl) propane,
2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane,
2,2-bis (4-hydroxyphenyl) butane, 2,
2-bis (4-hydroxy-3,5-diphenyl) butane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy-
3,5-diethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane and the like can be used, and these can be used alone or as a mixture. be able to.

The polyethylene terephthalate resin used as the component (B) in the present invention is 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, Other acid components include isophthalic acid,
Adipic acid, oxalic acid, etc., as a glycol component, propylene glycol as a glycol component,
1,4-butanediol, neopentyl glycol,
1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, etc., or a molecular weight of 4
00-6000 long chain glycols, ie, polyethylene glycol, poly-1,3-propylene glycol,
Polytetramethylene glycol or the like can be used in an amount of 20 mol% or less.

Further, the polyethylene terephthalate resin has an intrinsic viscosity of 0.36 to 1.60, particularly 0.45 to 5, measured at 25 ° C. using an O-chlorophenol solvent.
Those in the range of 1.15 are preferred. When the intrinsic viscosity is less than 0.36, the impact strength is poor, and when the intrinsic viscosity exceeds 1.60, the moldability becomes poor, and both are not preferred. If necessary, two or more kinds of polyethylene terephthalate resins having different intrinsic viscosities can be used in combination.

The polycarbonate resin and the polyethylene terephthalate resin of the component (B) may be used alone or in combination of both, and the amount of the mixture (in the case of combined use, the total amount is (A) polybutylene terephthalate). With respect to 100 parts by weight of the resin, it is 1 to 200 parts by weight, preferably 2 to 190 parts by weight. If less than 1 part by weight, the flame retardancy is impaired. It is not suitable because the moldability is impaired.

The phenolic resin used as the component (C) in the present invention is a (co) polymer having a plurality of phenolic hydroxyl groups, for example, a novolak-type, resol-type or heat-reactive resin, or Modified resins are mentioned. These are uncured resins with no added curing agent,
It may be a semi-cured resin or a cured resin. Above all, a phenol novolak resin that is non-thermally reactive without the addition of a curing agent is preferred in terms of flame retardancy, mechanical properties, and economic efficiency. The shape is not particularly limited, and any of pulverized products, granules, flakes, powders, needles, and liquids can be used. The phenolic resin may be used alone or as required.
More than species can be used.

The one type of novolak type phenol resin is charged into a reaction tank at a molar ratio of, for example, phenols to aldehydes of 1: 0.7 to 1: 0.9. After adding a catalyst such as hydrochloric acid, sulfuric acid, and toluenesulfonic acid, the mixture is heated and a reflux reaction is performed for a predetermined time. Thereafter, vacuum dehydration or standing dehydration is performed to remove generated water. It can be obtained by a method of removing phenols in the reaction. The co-condensed phenol resin obtained by using these resins or a plurality of raw material components can be used alone or in combination of two or more.

The resole type phenol resin has a molar ratio of phenols to aldehydes of 1: 1 to 1: 1.
It can be obtained by charging the reaction tank at a ratio of 1: 2, adding a catalyst such as sodium hydroxide, ammonia water, and other basic substances, and then performing the same reaction and treatment as the novolak-type phenol resin. it can.

Here, phenols are phenol, o
-Cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butylcatechol, catechol, isoeugenol, o-
Methoxyphenol, 4,4'-dihydroxyphenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate, 2,6-di-tert
-Butyl-p-cresol and the like. One or more of these phenols can be used.
On the other hand, aldehydes include formaldehyde, paraformaldehyde, polyoxymethylene, trioxane and the like. One or two or more of these aldehydes can be used as necessary.

The molecular weight of the phenolic resin is not particularly limited, but is preferably 200 to 2,000 in number average molecular weight.
In particular, those having a range of 400 to 1,500 are preferable because of excellent mechanical properties, molding workability, and economic efficiency. In addition, the molecular weight of the phenolic resin, tetrahydrafuran solution,
The measurement can be performed by gel permeation chromatography using a polystyrene standard sample.

The phenoxy resin used as the component (C) in the present invention is a (co) polymer obtained by reacting an aromatic dihydric phenol compound with epichlorohydrin at various mixing ratios. The molecular weights are different. The molecular weight of the phenoxy (co) polymer is not particularly limited, but the viscosity average molecular weight is 100 to 100,000.
A range of 0 is preferred.

Here, as the dihydric phenol compound,
2,2-bis (4-hydroxyphenyl) propane,
2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane,
2,2-bis (4-hydroxyphenyl) butane, 2,
2-bis (4-hydroxy-3,5-diphenyl) butane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy-
3,5-diethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) Methane and the like can be used, and these can be used alone or as a mixture.

The shape is not particularly limited, and any of pulverized products, granules, flakes, powders, needles, and liquids can be used. In addition, the phenoxy resin may be used as needed.
One or more species may be used, and if necessary, may be used in combination with one or more of the above-mentioned phenolic resins.

The phenolic resin (C) of the present invention and / or
Alternatively, the compounding amount of the phenoxy resin is 0.1 to 7 parts by weight per 100 parts by weight of the polybutylene terephthalate resin (A).
5 parts by weight, preferably 0.5 to 50 parts by weight, more preferably 1 to 50 parts by weight, less than 0.1 parts by weight,
If the flame retardancy is reduced, and if it exceeds 75 parts by weight, the impact strength is reduced, so that it is inappropriate.

The red phosphorus used as the component (D) in the present invention is unstable as it is, and has the property of gradually dissolving in water. It is preferably used. As a method for treating such red phosphorus, a method for pulverizing 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 is disclosed. , A method of micronizing red phosphorus, a method of catalytically suppressing oxidation of red phosphorus by adding a small amount of aluminum hydroxide or magnesium hydroxide to red phosphorus, coating red phosphorus with paraffin or wax, and contacting with moisture A method of stabilizing by mixing with ε-caprolactam or trioxane, and stabilizing by coating red phosphorus with a thermosetting resin such as a phenol-based, melamine-based, epoxy-based, and unsaturated polyester-based resin. Method, Stabilize red phosphorus by treating it with an aqueous solution of a metal salt such as copper, nickel, silver, iron, aluminum and titanium to deposit a metal phosphorus compound on the red phosphorus surface Aluminum hydroxide method, the red phosphorus to, magnesium hydroxide, titanium hydroxide, a method of coating by such as zinc hydroxide, iron red phosphorus surface, cobalt, nickel, manganese,
Examples include a method of stabilizing by coating with electroless plating with tin and the like, and a method of combining them. Preferably, a thermosetting resin such as phenol-based, melamine-based, epoxy-based, and unsaturated polyester-based red phosphorus is used. Or a method in which red 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.

Further, the average particle size of red phosphorus before being blended with the resin is 50% in view of the flame retardancy, impact strength and appearance of the molded product.
~ 0.01 μm, more preferably,
It is 45 to 0.1 μm. The red phosphorus (D) used in the present invention has a conductivity when extracted in hot water (that is, 100 g of pure water is added to 5 g of red phosphorus and extracted in an autoclave at 121 ° C. for 100 hours). , The conductivity measured with extracted water obtained by diluting the filtrate after red phosphorus filtration to 250 mL) is 0.1 to 1000 μS / cm from the viewpoint of flame retardancy and mechanical strength of the obtained molded product, and is preferably 0.
1 to 800 μS / cm, more preferably 0.1 to 50
0 μS / cm. Commercial products of such red phosphorus include “NOVA EXCEL 140” and “NOVA EXCEL F5” manufactured by Rin Kagaku Kogyo KK and equivalents of these commercial products.

The electric conductivity according to the present invention is 0.1 to 1000.
The addition amount of red phosphorus of μS / cm is 0.1 to 50 parts by weight, preferably 0.1 to 30 parts by weight, 0.1 to 25 parts by weight, more preferably 1 to 100 parts by weight of polybutylene terephthalate. To 20 parts by weight, more preferably 2 to 20 parts by weight. Among them, 3 to 15 parts by weight is particularly preferable.

The red phosphorus (D) of the present invention can be improved in stability, strength, heat resistance and the like during extrusion and molding by further adding a metal oxide as a stabilizer for red phosphorus. 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 and titanium oxide, among which cadmium oxide, cuprous oxide,
Cupric oxide and titanium oxide are preferred, and cuprous oxide, cupric oxide, and titanium oxide are more preferred, and titanium oxide is particularly preferred. In particular, titanium oxide has an effect not only as a stabilizer for red phosphorus, but also for improving the non-coloring property and the dispersibility of red phosphorus of the obtained molded article. 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 polybutylene terephthalate (A) from the viewpoint of mechanical properties and injection moldability. is there.

As the fibrous reinforcing material (E) used in the present invention, glass fibers, aramid fibers, carbon fibers and the like can be mentioned, and glass fibers are particularly preferable. The above-mentioned glass fiber is a chopped strand type or roving type glass fiber used for a normal PBT reinforcing material, and is a silane coupling agent such as an aminosilane compound or an epoxysilane compound, and / or bisphenol A glycidyl ether or novolac. 1 such as epoxy compound
Glass fibers treated with a sizing agent containing at least one kind of epoxy compound are preferably used.

The amount of the fibrous reinforcing material (E) is 1 to 100 parts by weight of the polybutylene terephthalate resin (A).
To 200 parts by weight, preferably 2 to 190 parts by weight,
If it is less than 1 part by weight, the flame retardancy is inferior. If it exceeds 200 parts by weight, the fluidity at the time of molding is greatly impaired and it is not suitable for practical production.

The polyolefin resin (F) used in the present invention is a polyethylene resin or a polyolefin-based copolymer, for example, high-density polyethylene, low-density polyethylene, ultra-low-density polyethylene, polyethylene copolymer and the above-mentioned polyolefin. A copolymer obtained by grafting or copolymerizing a resin with an acid anhydride or glycidyl methacrylate is mentioned.
More than seeds are used. Examples of the above polyethylene copolymer include ethylene as a monomer, and copolymerizable monomers such as propylene, butene-1, vinyl acetate, isoprene, butadiene, acrylic acid, and monocarboxylic acids such as methacrylic acid and the like. And copolymers produced by a conventional method such as ester acids, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid. Among them, copolymers obtained by grafting or copolymerizing an acid anhydride or glycidyl methacrylate on a polyolefin resin have good compatibility with PBT,
It is preferably used.

When (F) the polyolefin resin is compounded, the compounding amount thereof is preferably 1 to 100 parts by weight with respect to (A) 100 parts by weight of the polybutylene terephthalate resin.
It is particularly preferably 1 to 90 parts by weight or less, and if it is less than 1 part by weight, the effect of improving the impact strength is not sufficient, and if it exceeds 100 parts by weight, the flame retardancy decreases, which is not preferable.

The inorganic layered compound (G) used in the present invention includes:
An inorganic compound in which unit crystal layers are stacked one on top of the other and have a layered crystal structure and have cleavage properties. Specific examples of the inorganic layer compound include kaolinite, talc, smectite,
Examples include silicates such as vermiculite and mica, and phosphates such as zirconium phosphate and titanium phosphate.These inorganic layered compounds may be subjected to a coupling agent treatment or an organic treatment for ion exchange of inorganic ions between layers with organic ions. It may be performed. In addition, (G) the amount of the inorganic layered compound added is (A) polybutylene terephthalate 1
0 to 30 parts by weight, preferably 0 to 100 parts by weight.
-25 parts by weight, and exceeding 30 parts by weight is not preferable because the impact strength is impaired. The average particle size of the inorganic layered compound is 0.1 to 4 μm, preferably 0.3 to 3 μm.
If it exceeds 4 μm, the impact strength is impaired, which is not preferable.

The (H) fluorine-based resin used in 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, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer,
(Tetrafluoroethylene / ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride /
Ethylene) copolymers, among which polytetrafluoroethylene, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene ) Copolymers and polyvinylidene fluorides are preferred, especially polytetrafluoroethylene, (tetrafluoroethylene /
Ethylene) copolymers are preferred. The amount of the (H) fluorine-based resin is usually 0 to 100 parts by weight of the (A) polybutylene terephthalate resin in view of impact strength and moldability.
The amount is 10 to 10 parts by weight, preferably 0 to 8 parts by weight, more preferably 0 to 6 parts by weight. Exceeding 10 parts by weight is not preferable because the impact strength is impaired.

The (I) silicone compound used in the present invention is a silicone resin and / or silicone oil. With the silicone resin used in the present invention,
A polyorganosiloxane consisting of units represented by the following general formulas (1) to (4) and a chemically bonded siloxane unit selected from a mixture thereof.
Although a viscosity of 00 to 300,000,000 centipoise is preferable, the silicone resin is not limited thereto, as long as it is the above-mentioned silicone resin, and the product may be in the form of oil, powder, or gum. A methacle group and an amino group may be introduced.

[0039]

Embedded image (Here, R represents a group selected from a saturated or unsaturated monovalent hydrocarbon group, a hydrogen atom, a hydroxyl group, an alkoxyl group, an aryl group, a vinyl or allyl group, respectively.)

The silicone oil used in the present invention is represented by the following general formula (5). The silicone oil to be used preferably has a viscosity of 0.65 to 100,000 centistokes, but is not limited thereto as long as it is the above-mentioned silicone oil, and epoxy group, methacle group and amino group are introduced as functional groups. It may be.

Embedded image (Where R represents an alkyl group or a phenyl group, n
Is an integer of 1 or more. )

In the present invention, a silicone resin and / or a silicone oil can be used as the silicone-based compound, but a silicone resin is preferred from the viewpoint of flame retardancy and electrical properties.

The addition amount of the silicone compound (I) of the present invention is generally 0 to 10 parts by weight, preferably 0 to 10 parts by weight, per 100 parts by weight of the polybutylene terephthalate resin (A) in view of impact strength and moldability. The amount is 8 parts by weight, more preferably 0 to 6 parts by weight, and if it exceeds 10 parts by weight, the impact strength is impaired, which is not preferable.

The lubricant (J) 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. (J) The amount of the lubricant to be added is 0 to 30 parts by weight, preferably 0 to 25 parts by weight, per 100 parts by weight of (A) polybutylene terephthalate.
It is part by weight, and if it exceeds 30 parts by weight, the impact strength is impaired, which is not preferable.

When the polycarbonate resin is blended as the component (B), when a lubricant which is partially or entirely saponified or bonded with calcium or sodium is used as the lubricant, the contact contamination resistance and In order to suppress the deterioration of flame retardancy, it is preferable to use 0.1 to 5 parts by weight of (M) a phosphite-based stabilizer and / or a trivalent phosphorus compound. Here, the phosphite-based stabilizer is the same as the phosphite-based stabilizer described below as the component (L). In addition, examples of the trivalent phosphorus compound include, but are not limited to, phosphoric acid, triethyl phosphate, trimethyl phosphate, polyphosphoric acid, and phosphate, and phosphoric acid and triethyl phosphate are particularly preferably used. . The mixing amount thereof is 0.1 to 5 parts by weight, preferably 0.1 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the polybutylene terephthalate resin (A). Exceeding the portion is not preferable because the impact strength is impaired.

The (K) carbon black of the present invention is a black pigment that can be generally blended with plastics, and the amount of carbon black added is 0 to 20 parts by weight based on 100 parts by weight of (A) polybutylene terephthalate resin. Parts, preferably 0 to 18 parts by weight, more preferably 0 to 15 parts by weight. Exceeding 30 parts by weight is not preferable because the impact strength is impaired. The (L) hindered phenol-based stabilizer and / or phosphite-based stabilizer of the present invention is an additive effective for exhibiting extremely good heat aging resistance even when exposed to a high temperature for a long period of time.

Examples of such a hindered phenol-based stabilizer include triethylene glycol-bis [3-
(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], penta Erythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-tert-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-tert-butyl-4-hydroxybenzyl) benzene, bis or tris (3-tert-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.

Examples of the phosphite-based stabilizer include tris (2,4-di-t-butylphenyl) phosphite and 2,2-methylenebis (4,6-di-t-butylphenyl) octyl. Osphite, trisnonylphenyl phosphite, alkyl allyl phosphite, trialkyl phosphite, triallyl phosphite, pentaerythritol phosphite compound and the like can be mentioned. In the present invention, such a (L) hindered phenol-based stabilizer and / or phosphite-based stabilizer can be added as necessary, and the amount of addition at that time is usually polybutylene terephthalate. 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 resin (A);
Exceeding 0 parts by weight is not preferred because impact strength is impaired.

Further, the flame-retardant reinforced polybutylene terephthalate resin composition for an electric component housing of the present invention includes:
As long as the object of the present invention is not impaired, glass flakes, talc, kaolin, mica, and other plate-like inorganic fillers, sulfur-based and amine-based antioxidants and heat stabilizers, ultraviolet absorbers, mold release agents, plasticizers One or more conventional additives such as an agent, a UV inhibitor, a flame retardant other than the present invention, and a coloring agent including a dye or a pigment can be added.

The flame-retardant polybutylene terephthalate resin composition for an electric component housing of the present invention may be produced by a usual method. For example, (A) a polybutylene terephthalate resin, (B) a polycarbonate resin and / or a polyethylene terephthalate resin, (C) a phenol resin and / or a phenoxy resin, and (D) a conductivity of 0.1%.
1 to 1000 μS / cm red phosphorus, (E) fiber reinforcement,
And (F) a polyolefin resin, (G) an inorganic layered compound, (H) a fluorine resin, (I) a silicone compound, (J) a lubricant, (K) carbon black, (L) A resin composition is prepared by premixing additives such as a hindered phenol-based stabilizer and / or a phosphite-based stabilizer, or by supplying them to an extruder or the like without premixing and sufficiently kneading them. , Preferably, in terms of handling and productivity,
(A) Part of polybutylene terephthalate resin and / or (B) Part of polycarbonate resin and / or polyethylene terephthalate resin and (D) red phosphorus are once melt-kneaded to produce a resin composition having a high red phosphorus concentration. The remaining (A) polybutylene terephthalate resin and (B) polycarbonate resin and / or polyethylene terephthalate resin have the above-mentioned resin composition having a high red phosphorus concentration and other compounding components (including optional compounding additives).
Is prepared by melt-kneading.

The resin composition having a high red phosphorus concentration is as follows:
It 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 so-called chip, powder, or a mixture thereof. The polybutylene terephthalate resin, polycarbonate resin and / or polyethylene terephthalate resin to be mixed at the time of production of the master pellet is preferably in the form of pellets, but is not limited thereto. May be used. Furthermore, the form and size of the polybutylene terephthalate resin, the polycarbonate resin and / or the polyethylene terephthalate resin blended with the master pellet,
It is preferable that the shapes are substantially the same or similar to each other because they can be uniformly mixed. Further, when adjusting the resin composition having a high red phosphorus concentration, a part or all of (C) a phenol resin and / or a phenoxy resin or (F) a polyolefin resin may be adjusted in combination.

As a means for pre-mixing the resin composition of the present invention, dry blending may be mentioned, and in that case, mixing may be performed using a mechanical mixing device such as a Henschel mixer.
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, a single-screw extruder equipped with a “Unimelt” or “Dalmage” type screw, a twin-screw extruder, a triple-screw extruder, and a kneader of a kneader type may be used. it can.

The flame-retardant polybutylene terephthalate resin composition thus obtained can be molded by a usual method. For example, injection molding, extrusion molding, compression molding or the like is used to form a molded article used as an electric component housing. Can be.

The housing of the electric component having the electric contact opening / closing section, which is the application of the present invention, is the housing of the electric component having the electric contact opening / closing section such as a relay and a switch. Further, the electrical component housing is manufactured by an injection molding method by insert molding in which a part of the metal component is directly integrated with the housing molded product.

[0054]

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) Flame retardancy (UL94) Flame retardancy evaluation test specimens 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 was 1/32 "or 1/64". The smaller the thickness, the more severe the flame retardancy.

(2) Tracking Resistance (CTI) 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 CTI value is better when the applied voltage during the test is larger, and is measured at an applied voltage in the range of 0 V to 600 V. The above applied voltage is UL746A and is ranked in the following rank. CTI rank 0: 600V ≦ CTI value CTI rank 1: 400V ≦ CTI value <600V CTI rank 2: 250V ≦ CTI value <400V CTI rank 3: 170V ≦ CTI value <250V CTI rank 4: 100V ≦ CTI value <170V CTI rank 5: 0V ≦ CTI value <100V

(2) Resistance to Contact Contamination (Bleed-out Observation) 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 of 80 mm long × 80 mm wide × 3 mm thick was used. The plate was injection molded. Using the square plate, a PCT (pressure cooker test) test was performed at 121 ° C. × 100% RH at a temperature and humidity of 50 hours and 100 hours, and the surface of the square plate was visually observed for the presence or absence of bleed-out.

[Examples 1 to 39, Comparative Examples 1 to 13] Screw diameter 30 mm, L / D 35 with same direction rotating vent 2
Using a screw extruder (manufactured by Nippon Steel Works, TEX-30α)
(A) Polybutylene terephthalate resin having an intrinsic viscosity of 0.85 (25 ° C., o-chlorophenol solution) (hereinafter referred to as P
(B) a polycarbonate resin having an intrinsic viscosity of 0.65 (25 ° C., o-chlorophenol solution) (“Iupilon” S3 manufactured by Mitsubishi Engineering Plastics) with respect to 100 parts by weight of BT
Polyethylene terephthalate resin (hereinafter abbreviated as PET) having an intrinsic viscosity of 0.65 (25 ° C., o-chlorophenol solution);
(C) Phenol resin (PR5319 manufactured by Sumitomo Durres Co., Ltd.)
5) and / or phenoxy resin (“Phenotote” YP-50 manufactured by Toto Kasei Co., Ltd.), (D) red phosphorus (“Nova Excel 140” manufactured by Rin Kagaku Kogyo Co., Ltd.) and other additives are shown in Tables 1-2. The mixture was mixed at a ratio and added from the main filling section.

Further, a side feeder was provided in the middle of the filling portion and the vent portion, 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 above. Then, the mixture was melt-mixed under a kneading temperature of 280 ° C. and an extrusion condition of 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 by a usual method, ASTM D-6 is obtained by injection molding.
Test specimens such as a heat distortion temperature test specimen specified in No. 38 and a test specimen for evaluating flame retardancy based on UL94 were prepared. The measurement results of the tracking resistance, flame retardancy, and contact contamination resistance of each sample are shown in Tables 1 and 2 as in the above formulation.

The other additives of the present invention are as follows. (F) Polyolefin resin F-1: Polypropylene ("Mitsui Noblen" JS-G manufactured by Mitsui Toatsu Chemicals) F-2: Ethylene / glycidyl methacrylate copolymer ("Bond First-E" manufactured by Sumitomo Chemical) F-3: Ethylene / butene-1 / maleic anhydride copolymer ("MH5020" manufactured by DuPont-Mitsui Polychemicals) (G) Inorganic layered compound: Talc "HE-" manufactured by Takehara Chemical
5 "(H) Fluorine-based resin: polytetrafluoroethylene (" Teflon 6J "manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd.) (I) Silicone-based compound: silicone powder (DC4-7051 manufactured by Dow Corning Toray Silicone)

(J) Lubricant J-1: A lubricant in which a part of a fatty acid ester is converted into a calcium salt ("Hoechst Wax OP" manufactured by Hoechst Japan) J-2: A polycondensate consisting of ethylenediamine, stearic acid and sebacic acid (Kyoeisha) J-3: Acid anhydride-modified polyalkylene wax ("Mitsui High Wax 1105A" manufactured by Mitsui Petrochemical Industries) (K) Carbon black (Mitsubishi Chemical # 3050) (L) L -1: hindered phenol-based stabilizer, pentaerythryl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Ciba.
L-2: phosphite-based stabilizer, pentaerythritol-based phosphite compound ("PEP-24" manufactured by Asahi Denka Co., Ltd.)
G ″) (M) Trivalent phosphorus compound: reagent primary triethyl phosphate

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

As shown in Examples 1 to 14 in Table 1, PB
By blending T with a specific amount of PC and / or PET, a phenolic resin and / or a phenoxy resin, red phosphorus and a fiber reinforcing material of the present invention, it is excellent in tracking resistance and contact stain resistance, and excellent in difficulty. A resin composition suitable for a flammable electrical component housing is obtained. Further, as shown in Comparative Examples 1 to 11 in Table 1, PBT has P
When neither C nor PET is blended, when the blending amount of PC and / or PET is too large, or when any one of the essential components is not added, some of the above-mentioned excellent properties or flame retardancy are obtained. It is not a material that can be used as a housing for an electrical component having an electrical contact switch such as a relay or a switch.

From Examples 15 to 39 in Table 2, when the polyolefin resin specified in the present invention was used in combination, it was confirmed that the excellent characteristics of the present invention were maintained and the tracking resistance was greatly improved. Further, when any of talc and a lubricant was added to the composition of the present invention or a combination thereof, an effect of improving the appearance of a molded product while maintaining the excellent characteristics of the present invention was recognized. Further, by adding any one of or a combination of the fluorine-based resin, the silicone-based compound and the stabilizer to the composition of the present invention, further improved flame retardancy was obtained.

As shown in Examples 20, 26, and 39 in Table 2, PC was used as the component (B) of the present invention, and I-1 (a lubricant in which a part of the fatty acid ester was converted to calcium salt) was used as the lubricant. In the case where (3) is blended, it is preferable to blend a trivalent phosphorus compound or a phosphite-based stabilizer in combination for good contact stain resistance and flame retardancy. Example 23 in Table 2,
According to the present invention, such as 26, etc., excellent performance can be maintained even when carbon black is used in combination, so that it can be used as a black colored product. Also, as shown in Comparative Examples 12 and 13 in Table 2, when polypropylene is used as the polyolefin resin, flame retardancy and tracking resistance are greatly impaired, so that it is used as a housing for electrical components such as relays and switches. It was not a tolerable material.

[0067]

According to the present invention, PC and / or PBT are added to PBT.
Or, by blending PET, phenolic resin and / or phenoxy resin, red phosphorus and fiber reinforcement, for non-halogen flame-retardant polybutylene terephthalate for electrical component housings having excellent tracking resistance and contact contamination resistance A resin composition is obtained. The electric component having an electric contact switch such as a relay or a switch, which is an application of the present invention, is generally used by being incorporated in home appliances and OA equipment. The electric component housing having the opening / closing part is 2
It has a tracking resistance of CTI rank 2 or higher, which has no danger of fire even when used for 00V products, and further causes trouble of contact failure of relay or switch part due to bleed-out component generated from electric parts. And excellent contact resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/524 C08K 5/524 7/02 7/02 C08L 23/00 C08L 23/00 61/06 61 / 06 69/00 69/00 71/00 71/00 // (C08L 67/02 27:12 83:04) (72) Inventor Koji Yamauchi 1 Toray Co., Ltd., 9 Oe-cho, Minato-ku, Nagoya-shi, Aichi Nagoya Office F term (reference) 4J002 BB03Z BB04Z BB09Z BB10Z BD12U BD15U BD16U CC03Y CF06X CF07W CG01X CH08Y CP03U DA039 DA056 DH038 DJ038 DJ048 DJ058 DL007 EG039 EJ019 EP009 EW097 FB0FB FB0FB FB0

Claims (9)

[Claims] 1. A polybutylene terephthalate resin (A)
(B) polycarbonate resin and / or polyethylene terephthalate resin (1 to 200 parts by weight)
Parts by weight, (C) 0.1 to 75 parts by weight of phenolic resin and / or phenoxy resin, and (D) conductivity of 0.1 to 75 parts by weight.
0.1 to 50 parts by weight of red phosphorus of 1000 μS / cm (provided that conductivity is 5 g of red phosphorus, 100 mL of pure water is added, and
Extraction treatment at 100 ° C. for 100 hours, and filtration of red phosphorus to make the filtrate diluted to 250 mL.
1 to 200 parts by weight of fibrous reinforcing material, (F) any one of polyethylene resin and polyolefin-based copolymer
0-100 parts by weight of at least one kind of polyolefin resin, (G)
0 to 30 parts by weight of inorganic layered compound, (H) fluorine-based resin 0
10 to 10 parts by weight, (I) 0 to 10 parts by weight of silicone compound, (J) 0 to 30 parts by weight of lubricant, (K) 0 to 30 parts by weight of carbon black, (L) hindered phenol stabilizer and / or A flame-retardant polybutylene terephthalate resin composition for an electric component housing, comprising 0 to 10 parts by weight of a phosphite-based stabilizer. 2. The flame-retardant polybutylene terephthalate resin composition for an electrical component housing according to claim 1, wherein (D) red phosphorus is red phosphorus coated with a thermosetting resin. 3. The electric component housing according to claim 1, wherein the polyolefin resin comprises, as an essential component, a polyolefin copolymer obtained by copolymerizing maleic anhydride or glycidyl methacrylate. Flame retardant polybutylene terephthalate resin composition. 4. The flame-retardant polybutylene terephthalate resin composition according to claim 1, wherein the fibrous reinforcing material is glass fiber. 5. The flame retardant for an electrical component housing according to claim 4, wherein (F) the fibrous reinforcing material is glass fiber having a surface to which a sizing agent mainly composed of a silane coupling agent or an epoxy compound is adhered. Polybutylene terephthalate resin composition. 6. A case where a polycarbonate resin is blended as an essential component of (B) and a lubricant partially or wholly or partially saponified or bonded with calcium or sodium is blended as an essential component as a lubricant (J). The flame retardancy for an electrical component housing according to any one of claims 1 to 5, further comprising 0.1 to 5 parts by weight of (M) a phosphite-based stabilizer and / or a trivalent phosphorus compound. Polybutylene terephthalate resin composition. 7. An electrical component housing having an electrical contact opening / closing portion comprising the flame-retardant polybutylene terephthalate resin composition for an electrical component housing according to any one of claims 1 to 6. 8. A housing for an electrical component, comprising a flame-retardant polybutylene terephthalate resin composition for an electrical component housing according to any one of claims 1 to 6, wherein the metal is insert-molded and has an electrical contact opening / closing portion. 9. A housing for an electrical relay component or an electrical switch component, comprising a flame-retardant polybutylene terephthalate resin composition for an electrical component housing according to claim 1.