JP2000136297A - Flame-retarded resin composition and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retarded resin composition having excellent flame retardancy, tracking resistance, heat resistance, mechanical characteristics, etc., further having excellent recyclability, and useful for connectors, coil bobbins, etc., by adding a polycarbonate resin, etc., to polybutylene terephthalate resin. SOLUTION: This flame-retarded resin composition comprises (A) 100 pts.wt. of polybutylene terephthalate resin, (B) 0.1-100 pts.wt. of a polycarbonate resin, (C) 0.01-30 pts.wt. of red phosphorus having an electric conductivity of 0.1-1,000 μS/cm (the electric conductivity of extracted water obtained by adding 100 mL of pure water to 5 g of red phosphorus, subjecting the mixture to an extraction treatment at 121 deg.C for 100 hr, filtering off the red phosphorus, and then diluting the filtrate into 250 mL of the diluted water), and (D) 0.1-30 pts.wt. of a phosphoric ester of formula I [X is a group of formula II to IV; R1 to R8 are each H or a 1-5C alkyl; Ar1 to Ar4 are each an aromatic group or the like; Y is a direct bond or the like; (n) is >=0; (k), (m) are each 0-2, provided that (k)+(m)=0 to 2] (for example, a compound of formula V).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant resin composition having excellent recyclability. More specifically, thin molded products have excellent flame retardancy, tracking resistance, heat resistance, and mechanical properties (tensile strength and impact properties), and are also excellent in recyclability, and are suitable for mechanical mechanism parts, electrical and electronic parts, and automotive parts. And a flame-retardant resin composition.

[0002]

2. Description of the Related Art Polyester resins typified by polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexane dimethylene terephthalate, etc., make use of their excellent properties,
As an injection molding material, it is being used in a wide range of fields such as mechanical parts, electric and electronic parts, and automobile parts. On the other hand, since these polyester resins are inherently flammable, when used as industrial materials, in addition to the general balance of chemical and physical properties, safety against flames, that is, flame retardancy is required. There are many.

As a method of imparting flame retardancy to a polyester resin, a method of compounding a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant aid is generally used. However, this method 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.

Japanese Patent Application Laid-Open No. 10-168295 discloses the addition of a polycarbonate resin and red phosphorus as a method of making a polyester resin flame-retardant. However, although the flame-retardant resin composition obtained by the method disclosed in the publication is a useful flame-retardant resin composition not using a halogen-based flame retardant, it has a problem that fluidity is reduced, and polyester during compounding. Transesterification of the resin and the polycarbonate resin lowers the crystallinity, heat resistance, moldability, and tracking resistance, which is one of the electrical properties, causing the problem that the intrinsic properties of the polyester resin are impaired, and further significantly impairs the recyclability. There was a problem that.

[0006]

That is, the present invention uses a non-halogen flame retardant, has excellent flame retardancy and tracking resistance, has excellent fluidity, and is transesterified between a polyester resin and a polycarbonate resin. It is an object of the present invention to provide a flame-retardant resin composition having improved crystallinity, heat resistance, moldability, and recyclability.

[0007]

Means for Solving the Problems The present inventors have made intensive studies in view of the above situation, and as a result, by blending a polybutylene terephthalate resin with a polycarbonate resin and red phosphorus and a phosphoric acid ester having a specific conductivity. The present invention has found that a flame-retardant resin composition having highly excellent flame retardancy, excellent crystallinity, heat resistance, fluidity, moldability, tracking resistance, and excellent recyclability can be obtained. Reached.

That is, the present invention relates to a red resin having (A) 0.1 to 100 parts by weight of a polycarbonate resin and (C) a conductivity of 0.1 to 1000 μS / cm with respect to 100 parts by weight of a polybutylene terephthalate resin. Phosphorus 0.01 ~
30 parts by weight (However, conductivity is 5 g of red phosphorus and 100 g of pure water
Then, the extract was treated at 121 ° C. for 100 hours, and after filtration of red phosphorus, the solution obtained was diluted to 250 mL to obtain the conductivity of extracted water. (D) a flame-retardant resin composition prepared by mixing 0.1 to 30 parts by weight of a phosphoric ester represented by the following general formula (1);

[0009]

Embedded image

(In the above formula, R ^{1 to} R ⁸ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.)
Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ represent the same or different aromatic groups or aromatic groups substituted with halogen-free organic residues. Y is a direct bond, O, S,
Represents SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CHPh, and Ph represents a phenyl group. N is an integer of 0 or more. K and m are each an integer of 0 or more and 2 or less, and k +
m is an integer of 0 or more and 2 or less. The above-mentioned flame-retardant resin composition in which red phosphorus (C) is unground red phosphorus and red phosphorus coated with a thermosetting resin, and is charged with respect to 100 parts by weight of polybutylene terephthalate resin (A). The flame-retardant resin composition described above further comprising 5 to 140 parts by weight of the material, 100 parts by weight of the polybutylene terephthalate resin (A), and a fluororesin and / or 100 parts by weight.
Alternatively, 1 to 30 parts by weight of an olefin resin is further added to 100 parts by weight of the above-described flame-retardant resin composition and polybutylene terephthalate resin (A) further containing 0.01 to 10 parts by weight of a silicone compound. The flame-retardant resin composition described above, wherein the olefin-based resin is one or more selected from polyethylene and an ethylene-based copolymer, and the olefin-based resin is anhydrous. The triazine-based compound and cyanuric acid or isocyanuric acid are based on 100 parts by weight of the flame-retardant resin composition and polybutylene terephthalate resin (A) described above, which is an olefin resin copolymerized with maleic acid or glycidyl methacrylate. Salt 0.01
The resin composition according to the above, further comprising up to 30 parts by weight, and the present invention is a molded article made of the resin composition, wherein the molded article is a mechanical mechanism part, an electric / electronic part or an automobile part. The molded article is the above-mentioned molded article, wherein the molded article is a connector, a coil bobbin, a relay or a switch.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant resin composition of the present invention will be specifically described below. Examples of the polybutylene terephthalate resin (A) of the present invention include a high-molecular-weight thermoplastic polyester having an ester bond in a main chain, using terephthalic acid as an acid component and 1,4-butanediol as a glycol component. It is also possible to copolymerize other copolymerizable components. For example, as an acid component, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, oxalic acid, adipic acid, 1,4-cyclohexanedicarboxylic acid, etc., and as a glycol component, ethylene glycol, propylene glycol, 1,6-hexanediol, , 4-Cyclohexanedimethanol, bisphenol A, ethylene oxide adduct of bisphenol A, and the like can also be partially used.

The amount of copolymerization when the other components are copolymerized as described above is not particularly limited as long as the properties of polybutylene terephthalate are not significantly impaired, but is not limited to the total number of moles of dicarboxylic acid units and glycol units. On the other hand, it is preferably about 0 to 30 mol%, more preferably 0 to 2 mol%.
About 5 mol%, more preferably 0 to 20 mol%
It is about.

The polybutylene terephthalate used in the present invention has an intrinsic viscosity of 0.36 to 1.60, particularly 0.52 to 2, measured at 25 ° C. using an o-chlorophenol solvent.
Those in the range of 1.25 are preferred.

The polycarbonate resin (B) used in the present invention is obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester. The average molecular weight is in the range of 10,000 to 1,000,000. 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.

In the present invention, the amount of the polycarbonate resin (B) to be added is determined based on the polybutylene terephthalate resin 1
0.1 to 100 parts by weight, preferably 0.5 to 70 parts by weight, more preferably 1 to 60 parts by weight with respect to 00 parts by weight,
Particularly preferably, it is 5 to 50 parts by weight.

The red phosphorus (C) used in the present invention is unstable as it is, and gradually dissolves in water,
Since it has a property of gradually reacting with water, a material which has been treated to prevent this is preferably used. As such a method of treating red phosphorus, the method of pulverizing red phosphorus described in JP-A-5-229806 is not performed, and the red phosphorus is formed without forming a crushed surface having high reactivity with water or oxygen on the surface of red phosphorus. A method of finely dividing phosphorus, a method of catalytically suppressing 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 suppress contact with moisture Method, stabilization by mixing with ε-caprolactam or trioxane, phenol-based, melamine-based, epoxy-based red phosphorus,
A method of stabilizing by coating with a thermosetting resin such as an unsaturated polyester system, red phosphorus is copper, nickel,
A method in which a metal phosphorus compound such as silver, iron, aluminum and titanium is treated with an aqueous solution to precipitate and stabilize a metal phosphorus compound on the surface of red phosphorus.Aluminum hydroxide, magnesium hydroxide, titanium hydroxide, water Examples include a method of coating with zinc oxide or the like, a method of stabilizing the surface of red phosphorus by electroless plating with iron, cobalt, nickel, manganese, tin, or the like, and a method of combining them. A method of pulverizing red phosphorus without forming a crushed surface on the surface of red phosphorus without pulverization of red phosphorus, coating red phosphorus with thermosetting resin such as phenolic, melamine, epoxy, unsaturated polyester type By coating red phosphorus with aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide, etc. It is a method of stabilizing, particularly preferably a method of pulverizing red phosphorus without pulverizing red phosphorus and forming a crushed surface on the surface, a method of converting red phosphorus to phenolic, melamine, epoxy, unsaturated This is a method of stabilizing by coating with a thermosetting resin such as a polyester-based resin, or a method of combining both. Among these thermosetting resins, phenol-based thermosetting resin, red phosphorus coated with epoxy-based thermosetting resin can be preferably used from the viewpoint of moisture resistance, and phenol-based thermosetting resin is particularly preferable. Red phosphorus coated with resin.

Incidentally, unground red phosphorus, which is a preferred red phosphorus as the red phosphorus used in the present invention, refers to red phosphorus produced without forming a crushed surface.

The average particle size of red phosphorus before being mixed with the resin is 35 from the viewpoints of flame retardancy, mechanical properties, wet heat resistance, and chemical and physical deterioration of red phosphorus due to pulverization during recycling. The thickness is preferably from 0.01 to 0.01 μm, and more preferably from 30 to 0.1 μm.

The average particle size of red phosphorus can be measured by a general laser diffraction type particle size distribution analyzer. There are two types of particle size distribution analyzers: wet method and dry method.
Either one 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.

Although the average particle diameter of red phosphorus used in the present invention is as described above, red phosphorus having a large particle diameter contained in red phosphorus, that is, red phosphorus having a particle diameter of 75 μm or more is difficult. In order to significantly reduce the flammability, mechanical properties, wet heat resistance, and recyclability, red phosphorus having a particle size of 75 μm or more is preferably removed by classification. 75μm particle size
The above red phosphorus content is flame retardant, mechanical properties, wet heat resistance,
From the viewpoint of recyclability, it is preferably at most 10% by weight, more preferably at most 8% by weight, particularly preferably at most 5% by weight.
It is as follows. The lower limit is not particularly limited, but is preferably as close to 0 as possible.

Here, the particle size of red phosphorus is 75 μm.
The above-mentioned red phosphorus content can be measured by classification using a 75 μm mesh. That is, red phosphorus 100
g (g) when g is classified with a 75 μm mesh
Thus, the content of red phosphorus having a particle size of 75 μm or more is (A / 10
0) × 100 (%).

The conductivity of red phosphorus (B) used in the present invention when it is extracted in hot water (where the conductivity is determined by adding 100 mL of pure water to 5 g of red phosphorus, for example, in an autoclave to obtain 121%). Extraction at 100 ° C. for 100 hours, and diluting the filtrate after red phosphorus filtration to 250 mL, and measure the conductivity of the extracted water) is the moisture resistance, mechanical strength, tracking resistance, and recyclability of the obtained molded product. 0.1 ~
1000 μS / cm, preferably 0.1 to 800
μS / cm, more preferably 0.1 to 500 μS / c
m.

[0023] Examples of such preferred commercial products of red phosphorus include "NOVA EXCEL 140" and "NOVA EXCEL F5" manufactured by Rin Kagaku Kogyo KK.

In the present invention, the electric conductivity is 0.1 to 1000.
The addition amount of μS / cm red phosphorus (C) is 0.1 to 30 parts by weight, preferably 0.1 to 25 parts by weight, more preferably 1 to 100 parts by weight of polybutylene terephthalate resin.
To 20 parts by weight, more preferably 2 to 20 parts by weight. Particularly, 4 to 15 parts by weight is particularly preferable.

In the present invention, by further blending the phosphate ester (D), not only the flowability of the flame-retardant resin composition but also the transesterification of the polybutylene terephthalate resin and the polycarbonate resin can be suppressed. ,
It has been found that heat resistance, moldability, and recyclability are improved.

The (D) phosphate ester used in the present invention is represented by the following formula (1).

[0027]

Embedded image

First, the structure of the flame retardant represented by the above formula (1) will be described. In the formula (1), n is an integer of 0 or more, preferably 0 to 10, particularly preferably 0 to 5
It is. The upper limit is preferably 40 or less from the viewpoint of flame retardancy.

K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less, preferably, k and m are each an integer of 0 or more and 1 or less;
Particularly preferably, k and m are each 1.

In the formula (1), R ^{1 to} R ⁸ are the same or different and represent hydrogen or an alkyl group having 1 to 5 carbon atoms. Here, specific examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-isopropyl, neopentyl , Tert-
Pentyl group, 2-isopropyl, neopentyl, ter
t-pentyl group, 3-isopropyl, neopentyl, t
tert-pentyl group, neoisopropyl, neopentyl, tert-pentyl group and the like.
A methyl group and an ethyl group are preferable, and hydrogen is particularly preferable.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different aromatic groups or aromatic groups substituted by halogen-free organic residues. As the aromatic group, an aromatic group having a benzene skeleton, a naphthalene skeleton, an indene skeleton, or an anthracene skeleton is preferable, and an aromatic group having a benzene skeleton or a naphthalene skeleton is preferable. These may be substituted with an organic residue containing no halogen (preferably an organic residue having 1 to 8 carbon atoms), and the number of substituents is not particularly limited, but may be 1 to 3. preferable. Specific examples include a phenyl group,
Examples thereof include aromatic groups such as a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a naphthyl group, an indenyl group, and an anthryl group.A phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a naphthyl group are preferable, and a phenyl group is particularly preferable. , A tolyl group and a xylyl group are preferred.

Y is a direct bond, O, S, SO ₂ , C
(CH ₃ ) ₂ , CH ₂ , and CHPh, and Ph represents a phenyl group.

Among the above-mentioned phosphoric esters, those having the following structure are particularly preferred.

[0034]

Embedded image

In the above structural units, n is preferably from 0 to 5,
Particularly, 1 is preferable.

As such a phosphoric acid ester, PX-200 and TPP manufactured by Daihachi Chemical Co., Ltd. can be used.

In the present invention, a mixture of two or more phosphate esters may be used.

The amount of the phosphoric acid ester (D) to be used is generally 1 to 30 parts by weight, preferably 2 to 25 parts by weight, more preferably 3 to 20 parts by weight, based on 100 parts by weight of the polybutylene terephthalate resin.

If the amount of the phosphoric acid ester is too small, the effect of improving flame retardancy, heat resistance, moldability and recyclability is not recognized, and if it is too large, the mechanical properties and heat resistance of the molded article are impaired. Not preferred.

The flame-retardant resin composition of the present invention can significantly improve strength, rigidity, heat resistance and the like by further adding a filler. The shape of the filler may be any of fibrous, granular, etc., and may be used in combination.

Specific examples of such a filler include glass fiber, carbon fiber, metal fiber, aramid fiber, asbestos, potassium titanate whisker, walsteinite, glass flake, glass beads, talc, mica, clay,
Calcium carbonate, barium sulfate, titanium oxide and aluminum oxide, and the like, preferably glass fiber,
Among them, chopped strand type glass fibers are preferably used.

The amount of these additives is preferably from 5 to 140 parts by weight, particularly preferably from 5 to 100 parts by weight, per 100 parts by weight of the polybutylene terephthalate resin (A).

When the flame-retardant resin composition of the present invention further comprises a small amount of a fluorine-based resin and / or a silicone-based compound, not only the flame retardancy is improved, but also the tracking resistance,
It has been found that heat resistance and recyclability are improved. 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) copolymer And polytetrafluoroethylene, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, and (tetrafluoroethylene / ethylene) copolymer. , Polyvinylidene fluoride is preferred, and polytetrafluoroethylene, (tetrafluoroethylene / ethylene) copolymer is particularly preferred.

The silicone compound of the present invention is a silicone resin and / or silicone oil.

The silicone resin used in the present invention is:
Chemically bonded siloxane units selected from units represented by the following general formulas (2) to (5) and mixtures thereof (where R is a saturated or unsaturated monovalent hydrocarbon group, a hydrogen atom, A polyorganosiloxane comprising a group selected from a hydroxyl group, an alkoxyl group, an aryl group, a vinyl or an allyl group, and preferably a methyl group and / or a phenyl group. Although a resin having a viscosity of centipoise is preferable, the viscosity is not limited to the above silicone resin.

[0046]

Embedded image

The silicone oil used in the present invention is represented by the following general formula (6) (where,
R represents an alkyl group or a phenyl group, particularly preferably a methyl group and / or a phenyl group.
n is an integer of 1 or more. ). The silicone oil used preferably has a viscosity of 0.65 to 100,000 centistokes, but is not limited to the above silicone oil.

[0048]

Embedded image

In the present invention, a silicone resin and / or a silicone oil can be used as the silicone compound. However, flame retardancy, heat resistance, bleed-out resistance, contact contamination resistance, and deterioration of electrical properties after wet heat treatment. In view of the above, a silicone resin is preferable.

The amount of the fluorine resin and / or silicone compound of the present invention is usually 0.1 to 10 parts by weight based on 100 parts by weight of the polybutylene terephthalate resin (A) from the viewpoint of mechanical properties and moldability. , Preferably 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight.

The above-mentioned fluorine resin and silicone compound can be added together, but in this case, the total amount of the fluorine resin and silicone resin is
The amount is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and still more preferably 0.2 to 100 parts by weight based on 100 parts by weight of the polybutylene terephthalate resin (A).
３3 parts by weight.

Further, when the flame-retardant resin composition of the present invention is further added with an olefin resin, not only the flame retardancy is not reduced but also the mechanical properties and tracking resistance are improved, but also the heat resistance and recyclability are improved. Found to improve.

Examples of the olefin resin used in the present invention include polyethylene, ethylene copolymers, and other olefin (co) polymers. Among them, polyolefin resins having a low glass transition temperature are preferably used.

The polyethylene may be any of high-density polyethylene, low-density polyethylene, ultra-low-density polyethylene and the like.

The ethylene-based copolymer and the propylene-based copolymer are copolymers obtained by copolymerizing ethylene and a monomer copolymerizable therewith, among which ethylene-copolymerized at least 40 mol% is preferred. . Examples of copolymerizable monomers include α-olefins such as propylene and butene-1, vinyl acetate, isoprene, butadiene, and monocarboxylic acids such as acrylic acid and methacrylic acid, and esters thereof, maleic acid, fumaric acid, and itaconic acid. And a dicarboxylic acid or an acid anhydride thereof. These may be copolymerized in the main chain, or those which can be graft-polymerized may be graft-polymerized. These ethylene copolymers can be produced by a usual method.

Among the ethylene-based copolymers, a copolymer obtained by grafting an acid anhydride or glycidyl methacrylate to ethylene or ethylene and an α-olefin or copolymerizing it with a main chain is preferred. Specifically, a copolymer obtained by copolymerizing ethylene and glycidyl methacrylate, or a copolymer obtained by graft-polymerizing an acid anhydride such as maleic anhydride to an ethylene-propylene copolymer is preferable.

As the copolymer obtained by copolymerizing ethylene and glycidyl methacrylate, a copolymer of a vinyl monomer such as styrene and a vinyl cyanide monomer such as acrylonitrile was graft-copolymerized. It may be something.

Other olefin (co) polymers include (co) polymers of olefin compounds such as polypropylene and copolymers obtained by grafting acid anhydrides or glycidyl methacrylate to the olefin compounds or copolymerizing them with the main chain. Polymers and the like can be mentioned, and the latter is preferable, and among them, a copolymer obtained by copolymerizing styrene and glycidyl methacrylate is preferable.

Among these ethylene-based copolymers and other olefin-based (co) polymers, copolymers obtained by grafting or copolymerizing an acid anhydride or glycidyl methacrylate are preferably used because of their good compatibility with PBT.

These olefin resins can be used alone or in combination of two or more.

The amount of the olefin resin to be added is 1 to 30 parts by weight, preferably 2 to 25 parts by weight, particularly preferably 3 to 2 parts by weight, per 100 parts by weight of the polybutylene terephthalate resin.
0 parts by weight.

The flame-retardant resin composition of the present invention, when a salt of a triazine compound and cyanuric acid or isocyanuric acid is further added, suppresses not only flame retardancy but also deterioration in crystallinity, moldability and heat resistance. And improved tracking resistance, heat resistance, and recyclability.

In particular, it has been found that when a triazine compound and a salt of cyanuric acid or isocyanuric acid are used in combination, flame retardancy can be stably imparted even when the amount of PC resin or red phosphorus is reduced.

The triazine compound and the salt of cyanuric acid or isocyanuric acid used in the present invention are an adduct of cyanuric acid or isocyanuric acid and a triazine compound, usually in a ratio of 1: 1 (molar ratio). , Optionally having a composition of 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 (8).

[0066]

Embedded image

In the general formula (8), R ⁹ , R ¹⁰ , R
¹¹ and R ¹² are the same or different hydrogen, aryl group, alkyl group, aralkyl group, cycloalkyl group, or -C
ONH ₂ . Here, the aryl group has 6 to 6 carbon atoms.
Preferred are those having 15 carbon atoms, those having 1 to 10 carbon atoms as alkyl groups, those having 7 to 16 carbon atoms as aralkyl groups, and those having 4 to 15 carbon atoms as cycloalkyl groups. Further, R ¹³ is -NR ⁹ R ¹⁰ or -NR ¹¹ in the above formula.
Same group as R ¹² or those with 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, and the aralkyl group has 7 to 16 carbon atoms. And cycloalkyl groups having 4 to 15 carbon atoms are preferred.

Specific examples of R ⁹ , R ¹⁰ , R ¹¹ and R ¹² 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 ¹³ include an amino group, an amide group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a mono (hydroxymethyl) amino group and a 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 (8) 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 of the triazine compound and the cyanuric acid or isocyanuric acid was prepared by mixing a mixture of the triazine compound and the cyanuric acid or isocyanuric acid with a water slurry and mixing them well to form fine particles of both salts. Thereafter, this slurry is a powder obtained by filtering and drying, and is different from a mere mixture. The salt does not need to be completely pure, and a somewhat unreacted triazine-based compound or cyanuric acid or isocyanuric acid may remain.

Further, the average particle size of the salt before being mixed with the resin is determined based on the flame retardancy, mechanical strength and surface properties of the molded product.
It is preferably from 0 to 0.01 μm, more preferably from 80 to 0.01 μm.
10 μm. If the salt has poor dispersibility, a dispersant such as tris (β-hydroxyethyl) isocyanurate may be used in combination. The average particle size of the salt can be measured by a general laser diffraction type particle size distribution analyzer.

The amount of the above salt is usually 0.01 to 100 parts by weight of the polybutylene terephthalate resin (A).
It is 30 parts by weight, preferably 0.1 to 25 parts by weight, more preferably 0.5 to 20 parts by weight.

The flame-retardant resin composition of the present invention can further improve the stability, strength, heat resistance and the like during extrusion and molding by 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 to improve the non-coloring property of the obtained resin composition and the dispersibility of red phosphorus.

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.

It has been found that when the flame retardant resin composition of the present invention is further used in combination with a hindered phenol-based stabilizer, extremely good hydrolysis resistance can be maintained even when exposed to a high temperature for a long period of time. As such a stabilizer, for example, triethylene glycol-bis [3- (3-t-butyl-
5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 2,2-thio-diethylenebis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-t-butyl-4-hydroxybenzyl) benzene, bis or tris (3-t-butyl-6-methyl-4-hydroxyphenyl) propane, N, N'-hexamethylenebis (3,5-di- t-butyl-4-hydroxy-hydrocinnamamide), N, N'-trimethylenebis (3,5-
Di-t-butyl-4-hydroxy-hydrocinnamide) and the like. In the present invention, such a hindered phenol-based stabilizer can be added as needed, and the amount of the hindered phenol-based stabilizer added at that time is usually 100% by weight of the polybutylene terephthalate resin (A). 0.01 to 3 parts by weight, preferably 0.02 to 2 parts by weight, more preferably 0.03 to 3 parts by weight,
0.5 parts by weight.

The flame-retardant resin composition of the present invention may contain a thermoplastic resin other than the polybutylene terephthalate resin, polycarbonate resin and olefin resin used in the present invention.

For example, polystyrene resins such as polystyrene resin, styrene / acrylonitrile copolymer, acrylonitrile / butadiene / styrene copolymer (ABS resin), polyester resins other than polybutylene terephthalate resin, liquid crystal polyester resin, polyamide resin, polyphenylene Oxide resin, modified polyphenylene oxide resin, polyphenylene sulfide resin, polyoxymethylene resin, phenoxy resin, phenol resin,
Elastomers such as polyester polyether elastomers and polyester polyester elastomers, or mixtures of two or more of these thermoplastic resins, include polyester resins other than polystyrene resins, modified polyphenylene oxide resins, polybutylene terephthalate resins, polyamide resins, and phenoxy resins 1 selected from resin, polyphenylene sulfide resin, and phenol resin
A species or a mixture of two or more species is preferable, and more preferably, one or a mixture of two or more species selected from a polyester resin other than a polystyrene resin, a polybutylene terephthalate resin, a polyamide resin, a phenoxy resin, and a phenol resin.

The amount of the thermoplastic resin to be added is not particularly limited as long as the effects of the present invention are not impaired, but is not limited to 0.1 part by weight based on 100 parts by weight of the polybutylene terephthalate resin.
It is 1 to 100 parts by weight, preferably 0.5 to 80 parts by weight, more preferably 1 to 70 parts by weight.

Further, the flame-retardant resin composition of the present invention may contain phosphorus-based or sulfur-based antioxidants other than hindered phenols, heat stabilizers, etc. as long as the object of the present invention is not impaired.
One or more ordinary additives such as an ultraviolet absorber, a lubricant, a releasing agent, and a coloring agent including a dye or a pigment can be added.

The amount of these additives is 0.01 to 3 parts by weight, preferably 0.02 to 2 parts by weight, more preferably 0.03 to 2 parts by weight, based on 100 parts by weight of the polybutylene terephthalate resin.
0.5 parts by weight.

The method for producing the resin composition of the present invention is not particularly limited. For example, it can be produced by melt-kneading the above-mentioned components, other components, resins and the like using a melt-kneading machine such as a single-screw extruder, a twin-screw extruder or a multi-screw extruder.

The flame-retardant resin composition and the molded article thus obtained can be usually molded by a known method, such as injection molding, extrusion molding, compression molding, blow molding, vacuum molding, press molding, calender molding, and foam molding. And molded articles of all shapes such as sheets and films. Among them, it is particularly suitable for use in injection molded products.
It is also suitable for molded articles having a complicated shape such as molded articles having a weld portion and a hinge section, insert molded articles, and thin molded articles, and is suitable for various mechanical mechanism parts, electric and electronic parts, or automobile parts.

For example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors,
Variable condenser case, optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, housing, semiconductor, liquid crystal display parts, FDD carriage , FDD chassis, HDD parts, motor brush holders, parabolic antennas, electrical and electronic parts such as computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio parts・ Sound equipment parts such as laser discs and compact discs, lighting parts,
Home, office electrical product parts, office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, oilless bearings, such as refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. , Stern bearings, underwater bearings, and other various bearings, motor parts, mechanical parts such as lighters, typewriters, microscopes, binoculars, cameras,
Optical equipment represented by watches, precision machinery-related parts, alternator terminals, alternator connectors,
IC regulator, potentiometer base for light deer, various valves such as exhaust gas valve, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel pump,
Engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, thermostat for air conditioner Base, Heating hot air flow control valve, Brush holder for radiator motor, Water pump impeller, Turbine vane, Wiper motor related parts, Distributor, Starter switch, Starter relay, Wire harness for transmission,
Window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation board, step motor rotor, lamp socket, lamp reflector,
It is useful for various applications such as lamp housings, brake pistons, solenoid bobbins, engine oil filters, and ignition device cases. Among the above, the features of the present invention, in particular, the flame retardancy, mechanical properties, and heat resistance of thin molded products ,
It can be suitably used for connectors, coil bobbins, relays, and switches as parts that make use of tracking resistance, fluidity, and recyclability.

[0086]

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) Thermal Characteristics Using DSC7 manufactured by PERKIN ELMER, 50
After raising the temperature range of ３００300 ° C. at a rate of 20 ° C./min, holding for 1 minute, lowering the temperature range of 300-50 ° C. at 20 ° C./min, holding for 1 minute, and then again at 50-300 ° C.
The peak top observed when the temperature range was increased at a rate of 20 ° C./min was defined as the melting point (Tm) of the measurement sample.

The melting point (Tm) obtained by the above measurement
The temperature range from 50 to 300 ° C. was raised at a rate of 20 ° C./min, and then the melting point Tm−20 obtained at 100 ° C./min.
After the temperature was lowered to ° C, the exothermic peak obtained when the sample was held for 30 minutes was measured. From the exothermic peak area, the half-crystallization time (t1 / 2) (the time when the amount of heat of fusion is half of the total amount of heat of fusion) was calculated, and the half-crystallization time was used as a measure of the crystallization rate. The smaller this value is, the faster the crystallization speed is.

(2) Mechanical properties ASTM was applied to dumbbell test pieces obtained by injection molding.
The tensile yield strength was measured according to D-638.

(3) Impact Properties Izod impact strength of 1/4 inch (with notch) was measured according to ASTM D-256.

(4) Heat resistance (deflection temperature under load) ASTM
According to -D648, the deflection temperature under load at a load of 1.82 MPa was measured.

(5) Flame Retardancy The flame retardancy test specimen (1/32 inch thick) obtained by injection molding was evaluated for flame retardancy in accordance with the evaluation criteria defined in UL94. The flame retardancy level is V-0>V-1>
V-2> HB. The sum of the burning times of the five samples was used as an index of flame retardancy.

(6) Tracking Resistance A 80 mm × 80 mm, 3 mm thick test piece obtained by injection molding was subjected to a tracking resistance test in accordance with the IEC112 test standard, and the CTI (Comparative T) was tested.
(Tracking Index) was measured. (7) Fluidity Injection molding of a test piece (1/32 inch thick) for evaluating flame retardancy using a Toshiba Machine's IS55EPN injection molding machine at a molding temperature of 270 ° C and a mold temperature of 80 ° C. The minimum molding pressure was used as a measure of fluidity. The smaller this value is, the better the fluidity is.

(8) Evaluation of Recycling The injection molded product was repeatedly crushed / molded, and finally, the thermal properties, deflection temperature under load, and mechanical properties were measured using the fifth burning test piece, and the recyclability was evaluated. Judgment was made from the following indicators. ΔTm = (melting point of test piece at the first molding) − (melting point of test piece at the fifth molding) The larger the value, the lower the recyclability. .DELTA.t1 _{/ 2 =} (half-crystallization time of the fifth test piece (t
_1/2 )-(half-crystallization time of the first test specimen). The larger the value, the lower the recyclability. [Delta] Load deflection temperature = (Load deflection temperature of test piece at the first molding)-(Load deflection temperature of test piece at the fifth molding).
The larger the value, the lower the recyclability.・ Strength retention = [(tensile strength of test piece after molding 5) /
(Tensile strength of test piece at first molding)] The strength retention rate is calculated from × 100, and the smaller the value, the lower the recyclability.

Reference Example 1 Red phosphorus high concentration product (D-1) Polybutylene terephthalate resin (hereinafter abbreviated as PBT)
100 parts by weight of Toray PBT1100S (manufactured by Toray Industries, Inc.), red phosphorus (“NOVAEXCEL 140” manufactured by Rin Kagaku Kogyo Co., Ltd.): unmilled red phosphorus was coated with a thermosetting resin, and the average particle size was 29. 7 μ, 5 g of red phosphorus, 100 mL of pure water,
Extraction treatment at 121 ° C. for 100 hours in an autoclave,
The solution after red phosphorus filtration was diluted to 250 mL, and 100 parts by weight of a conductivity meter (a conductivity of 200 μm S / cm as measured using a conductivity meter (manufactured by Yokogawa Electric Corp., personal SC meter)) were mixed. 30m screw diameter
melt extrusion at a resin temperature of 280 ° C. using a coaxially rotating twin screw extruder (manufactured by Nippon Seiko Steel Co., Ltd., TEX-30) having a m / L / D = 45.5, and a polybutylene terephthalate resin having a high red phosphorus concentration (D -1) was prepared.

Reference Example 2 Red phosphorus high concentration product (D-2) Polybutylene terephthalate resin (hereinafter abbreviated as PBT)
100 parts by weight of Toray PBT1100S (manufactured by Toray Industries, Inc.), and red phosphorus (“Nova Red” manufactured by Rin Kagaku Kogyo KK)
120): Coated ground red phosphorus with thermosetting resin, average particle size 3
8 μm, conductivity of 1200 μS / cm) and 100 parts by weight of the mixture.
Using a coaxial rotary twin-screw extruder (LEX / DEX = 45.5) (manufactured by Nippon Seiko Co., Ltd., TEX-30), the resin is melt-extruded at a resin temperature of 280 ° C. to obtain a polybutylene terephthalate resin having a high red phosphorus concentration (D-2). ) Manufactured.

The additives used in Examples and Comparative Examples are shown below.・ Polybutylene terephthalate resin (Toray PBT110
0S (manufactured by Toray Industries, Inc.)-Polycarbonate resin ("Iupilon" S3000)
(Mitsubishi Engineering Plastics Co., Ltd.) Phosphoric acid ester (Resorcinol-type bisphosphate “PX-200” manufactured by Daihachi Chemical Co., Ltd.) Glass fiber (“CS3J948” manufactured by Nitto Boseki Co., Ltd.) -Cyanuric acid salt, melamine cyanurate ("MC440" manufactured by Nissan Chemical Industries, Ltd.) (abbreviated as MC salt in Table 1)-Olefin-based resin (ethylene / glycidyl methacrylate copolymer (Sumitomo Chemical's "Bond First-E") ") ・ Fluorine-based resin, polytetrafluoroethylene (“ Teflon 6J ”manufactured by DuPont-Mitsui Fluorochemicals) ・ Silicone resin“ DC4-7105 ”(Toray
Dow Corning Silicone Co., Ltd.) was used. Stabilizer (pentaerythryl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] ("IR-101 manufactured by Ciba-Geigy Corporation")
0 ″)) The amount of glass fiber in the resin composition was 30% by weight with respect to 100% by weight of the entire resin composition.

Examples 1 to 6 and Comparative Examples 1 to 3 The PC resin, the high-concentration red phosphorus product produced in the reference example, the phosphoric acid ester and various additives were mixed in the mixing ratio shown in Table 1 with respect to PBT. Screw diameter 30mm, L / D45.
5 twin-screw extruder (TEX-3, manufactured by Nippon Steel Corporation)
0: The screw uses two screws of 3.5 mm that engage with each other with two threads, and screw elements consisting of 10 kneading disks inclined at 45 degrees with L / D = 4 are provided in reverse order. And melt extruded at a resin temperature of 280 ° C. using a reverse kneading element having a strong kneading force.

After the obtained pellets were dried, the pellets were
Using an S55EPN injection molding machine, a molding temperature of 270 ° C.
ASTM D-638, D-2 under the condition of mold temperature 80 ° C
56, a tensile test specimen, an impact test specimen, a load deflection test specimen specified in D-648, and a test specimen (1/32 inch thick) for evaluating flame retardancy based on UL94. When forming the combustion test piece, the minimum molding pressure was measured, and this value was used as a measure of fluidity.

As for a sample for recycling evaluation, an injection-molded product was pulverized by a pulverizer and then introduced into the injection molding machine again. This operation was repeated, and a test piece finally obtained by the fifth injection molding was used as a sample for evaluating recyclability.

The thermal properties of each sample (melting point, half-crystallization time), flame retardancy, tensile strength, impact strength, deflection temperature under load and the thermal properties of the recycled product (melting point, half-crystallization time) The tensile strength was measured. Table 1 shows the results.

[0102]

[Table 1]

From the comparison between Example 1 and Comparative Example 1, when the PC resin, red phosphorus, and phosphoric acid ester were blended, they were excellent in flame retardancy, fluidity, mechanical properties, high deflection temperature under load, and excellent heat resistance. Further, the crystallization speed is high because the half-crystallization time is short. Furthermore, the change in the melting point and the change in the half-crystallization time of the recycled product are small, and the decrease in the deflection temperature under load and the decrease in the strength are small, indicating that the flame retardant resin composition is excellent in recyclability. It is also found that the tracking resistance is improved by the addition of the phosphate ester.

On the other hand, in Comparative Example 1 in which no phosphate ester was added, a decrease in melting point, a decrease in crystallization rate, and a decrease in heat resistance were observed, and it was also found that tracking resistance and recyclability were poor.

As shown in Example 2 and Comparative Example 2, P
When the addition amount of the C resin was increased, the effect of adding the phosphoric acid ester was remarkable. In Comparative Example 2 in which the phosphoric acid ester was not added, the melting point was reduced and the crystallization rate was lower than in Example 2 in which the phosphoric acid ester was added. It can be seen that the decrease in heat resistance and heat resistance are large, and the recyclability and tracking resistance are also inferior.

From the comparison between Example 1 and Comparative Example 3, it can be seen that when red phosphorus having high conductivity is used, flame retardancy and fluidity are excellent, but recyclability is poor.

In Example 3, Teflon was further added to the composition of Example 1. It can be seen that by adding a small amount of Teflon, not only the burning time is shortened, but also the half-crystallization time is short (the crystallization speed is fast), the deflection temperature under load, the tracking resistance and the recyclability are improved.

In Example 4, an ethylene / glycidyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd .;
E ").

It can be seen that the blending of the polyolefin resin improves the mechanical properties (impact strength), the tracking resistance, and the recyclability without lowering the flame retardancy.

In Example 5, as compared with the composition of Example 1, the amounts of PC resin and red phosphorus were reduced instead of incorporating melamine cyanurate. As a result, even if the amount of PC and the amount of red phosphorus are reduced, flame retardancy V-0 is obtained, the half-crystallization time is shortened (the crystallization speed is high), the deflection temperature under load (heat resistance), It can be seen that the tracking property is improved and the recyclability is further improved.

In Example 6, a silicone resin was used as the silicone compound instead of the Teflon resin of Example 5. As a result, the same effect as the Teflon resin was obtained with the silicone resin, and the impact strength and the recyclability tended to be improved.

The flame-retardant resin composition of the present invention has not only high flame retardancy but also excellent mechanical properties (tensile strength, impact strength), heat resistance, tracking resistance and fluidity. I have. Usually, alloys of PBT and PC cause a decrease in heat resistance, a decrease in crystallinity, and a decrease in crystallization rate.
The flame-retardant resin composition of the present invention has a high crystallization rate and retains the original characteristics of the polybutylene terephthalate resin.
Little decrease in strength. In recent years, connectors, coil bobbins, relays, and switch parts have been required to have high flame retardancy, mechanical properties, heat resistance, and recyclability, and the flame retardant resin composition of the present invention is particularly suitable for these applications. It is a resin composition.

[0113]

(1) The flame-retardant PBT resin composition comprising the PC resin of the present invention and red phosphorus and a phosphoric acid ester having a specific conductivity is different from other conventionally known red phosphorus-containing flame-retardant resin compositions. In addition to having high flame retardancy, it also has excellent mechanical properties (strength, impact), heat resistance, tracking resistance, fluidity, and has the crystallization characteristics of PBT resin, Also has excellent recyclability. (2) The flame-retardant resin composition obtained by the present invention is useful for mechanical parts, electric / electronic parts, and automobile parts utilizing these characteristics, and is particularly suitable for connectors, coil bobbins, relays, and switch parts.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 7/14 C08K 7/14 9/04 9/04 // H01F 41/12 H01F 41/12 F H01H 9 / 02 H01H 9/02 Z H01R 13/46 301 H01R 13/46 301B (C08L 67/02 69:00 27:12 23:00)

Claims (10)

[Claims] 1. A polybutylene terephthalate resin (A)
(B) 0.1 parts by weight of polycarbonate resin
-100 parts by weight, (C) conductivity is 0.1-1000 μS
0.01-30 parts by weight of red phosphorus (conductivity: 5 g of red phosphorus, 100 mL of pure water, extraction at 121 ° C. for 100 hours, and filtration of the red
The conductivity of extraction water diluted to 0 mL is defined as the conductivity. (D) A flame-retardant resin composition comprising 0.1 to 30 parts by weight of a phosphoric ester represented by the following general formula (1). Embedded image (In the formula, R ¹ to R ⁸ represent identical or different hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The Ar ^1,
Ar ² , Ar ³ , and Ar ⁴ represent the same or different aromatic groups or aromatic groups substituted with halogen-free organic residues. Y is a direct bond, O, S, SO ₂ , C
(CH ₃ ) ₂ , CH ₂ , and CHPh, and Ph represents a phenyl group. N is an integer of 0 or more. K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less. ) 2. The flame-retardant resin composition according to claim 1, wherein the red phosphorus (C) is unground red phosphorus and red phosphorus coated with a thermosetting resin. 3. A polybutylene terephthalate resin (A) 1
3. The flame-retardant resin composition according to claim 1, further comprising 5 to 140 parts by weight of a filler based on 00 parts by weight. 4. A polybutylene terephthalate resin (A) 1
The flame-retardant resin composition according to any one of claims 1 to 3, further comprising 0.01 to 10 parts by weight of a fluorine-based resin and / or a silicone-based compound with respect to 00 parts by weight. 5. A polybutylene terephthalate resin (A) 1
The flame-retardant resin composition according to any one of claims 1 to 4, further comprising 1 to 30 parts by weight of an olefin resin based on 00 parts by weight. 6. The flame-retardant resin composition according to claim 6, wherein the olefin resin is one or more selected from polyethylene and an ethylene copolymer. 7. The flame-retardant resin composition according to claim 5, wherein the olefin resin is an olefin resin obtained by copolymerizing maleic anhydride or glycidyl methacrylate. 8. A polybutylene terephthalate resin (A) 1
The resin composition according to any one of claims 1 to 8, further comprising 0.01 to 30 parts by weight of a salt composed of a triazine compound and cyanuric acid or isocyanuric acid with respect to 00 parts by weight. 9. A molded article comprising the resin composition according to claim 1, wherein the molded article is a mechanical mechanism part, an electric / electronic part or an automobile part. 10. The molded article according to claim 9, wherein the molded article is a connector, a coil bobbin, a relay, or a switch.