JP2000109686A - Flame retardant resin composition and molded article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain flame retardant resin compositions with improved flowability, thin wall flame retardance and impact resistance, heat stability, sliding properties, surface appearance and metal corrosion resistance, and molded articles thereof. SOLUTION: Flame retardant resin compositions are obtained by incorporating 0.1-30 pts.wt. one or more metal hydroxides selected from a hydroxide of a group II metal and a hydroxide of a group II metal and 0.01-30 pts.wt. red phosphorus into 100 pts.wt. resin composition composed of 100 pts.wt. polyamide resin and 0.05-30 pts.wt. liquid crystalline resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to improved fluidity, thin-walled flame retardancy and impact resistance, thermal stability, slidability, surface appearance, improved metal corrosion resistance and rigidity, and warpage of molded products. The present invention relates to an improved flame-retardant resin composition and a molded product thereof.

[0002]

2. Description of the Related Art Thermoplastic resins such as polyamide resins, polyester resins, polycarbonate resins, and polyphenylene oxide resins make use of their excellent characteristics.
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 thermoplastic resins are inherently flammable, in order to be used as industrial materials, in addition to the general balance of chemical and physical properties, fire safety, that is, flame retardancy is required. Often.

As a method of imparting flame retardancy to a thermoplastic resin, a method of compounding a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant auxiliary into the resin is generally used. However, this method tends to generate a large amount of smoke during combustion. Further, the resin composition containing the halogen-based flame retardant has a problem that the electric characteristics are deteriorated.

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

Heretofore, as a method of making a thermoplastic resin flame-retardant 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 sufficient flame retardancy, it is necessary to add a large amount of the above-mentioned hydrated metal compound, which has a disadvantage that the inherent properties of the resin are lost.

On the other hand, as a method for flame retarding a polyamide resin without using such a hydrated metal compound, addition of red phosphorus is disclosed in JP-A-60-168775 and JP-A-61-219706. JP-A-63-89567, JP-A-1-129061, JP-A-2-16
No. 9666, JP-A-3-197553, JP-A-6-145504, JP-A-6-263983 and the like. Japanese Patent Application Laid-Open No. 5-320486.
Japanese Patent Application Laid-Open Publication No. H11-139,086 discloses a method for improving flame retardancy and electric properties by adding red phosphorus.

[0007]

However, any resin composition exhibits excellent flame retardancy in a thick (1/16 inch) molded product, but thin resin materials required in recent years have become thinner. (1/32 inch or less) There was a problem that the flame retardancy of the molded product could not be obtained sufficiently. In addition, the resin composition obtained by the method described in JP-A-5-320486 has a problem that the flame retardancy is insufficient and the effect of improving the electrical properties is not sufficient.

Further, the resin composition obtained by any of the methods has a problem that the mechanical properties are deteriorated and the flame retardant bleeds out during dry heat treatment.

The present invention solves the above problems and provides a flame-retardant resin composition having improved fluidity, thin-walled flame retardancy and impact resistance, thermal stability, slidability, surface appearance, and metal corrosion resistance. And to obtain a molded product thereof.

[0010]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention relates to (1) 100 parts by weight of a resin composition (C) composed of 100 parts by weight of a polyamide resin (A) and 0.05 to 30 parts by weight of a liquid crystal resin (B), and One or more metal hydroxides selected from hydroxides and hydroxides of Group III metals (D) in an amount of 0.1 to 30 parts by weight and red phosphorus (E) in an amount of 0.01 to 30 parts by weight. (2) The conductivity of red phosphorus is 0.1 to 1
(3) 100 to 100 parts by weight of the resin composition (D), further containing 0.5 to 300 parts by weight of a filler. (1) The flame-retardant resin composition according to (2), (4) the flame-retardant resin according to any one of (1) to (3), wherein the liquid crystalline resin (B) contains an ethylenedioxy unit. The composition, (5) the flame-retardant resin according to any one of the above (1) to (4), wherein the metal hydroxide (D) is at least one selected from magnesium hydroxide, calcium hydroxide, and aluminum hydroxide. (6) The composition according to (1) to (6), which has a thickness of 0.8 mm in the UL-94 standard and a flame retardancy of V-0.
(5) The flame-retardant resin composition according to any one of (5), (7) a part of the resin component to be finally added, and a metal hydroxide and / or
Alternatively, red phosphorus is once melt-kneaded to prepare a resin composition having a concentration higher than the amount of metal hydroxide and / or the amount of red phosphorus to be actually blended into the flame-retardant resin composition.
(8) A method for producing a flame-retardant resin composition, which comprises producing the flame-retardant resin composition according to any one of (1) to (6).
A molded article comprising the flame-retardant resin composition according to any one of the above (1) to (6), wherein the molded article is a mechanical mechanism part, an electric / electronic part or an automobile part;
(9) A molded article comprising the flame-retardant resin composition according to any one of the above (1) to (6), wherein the molded article has a plate shape or a box shape and a thickness of 1.0 mm or less. It is an object of the present invention to provide a molded article characterized by having a thin portion of 10% or more based on the total surface area of the molded article.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant resin composition of the present invention will be specifically described below. The polyamide resin (A) used in the present invention is a nylon containing amino acids, lactams or diamines and dicarboxylic acids as main raw materials. Representative examples of the raw materials include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, lactams such as ε-aminocaprolactam, ω-laurolactam, tetramethylenediamine, Hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, meta Xylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane,
1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane , 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, and other aliphatic, alicyclic, and aromatic diamines, and adipic acid, speric acid, azelaic acid, and sebacic acid , Dodecane diacid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, aliphatics such as hexahydroisophthalic acid, Alicyclic and aromatic dicarboxylic acids are exemplified by the present invention. Information, it is possible to use nylon homopolymers or copolymers derived from these raw materials each alone or in the form of mixtures.

In the present invention, particularly useful polyamide resins are nylon resins having a melting point of 200 ° C. or more and excellent in heat resistance and strength. Specific examples thereof include polycaproamide (nylon 6) and polyhexamethylene. Adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polynonamethylene methylene terephthalamide (nylon 9T), Polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66
/ 6T), polyhexamethylene terephthalamide / polycaproamide copolymer (nylon 6T / 6), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polydodecamide / polyhexamethylene terephthalamide copolymer (Nylon 12 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 /
6T / 6I), polyhexamethylene terephthalamide /
Polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / poly (2-methylpentamethylene terephthalamide) copolymer (nylon 6T / M5T), polyxylylene adipamide (nylon XD6) and the like Mixtures and copolymers are exemplified.

Particularly preferred are nylon 6, nylon 66, nylon 610, nylon 46, nylon 9T, nylon 6/66 copolymer, nylon 6
/ 12 copolymer, nylon 6T / 6 copolymer, nylon 66 / 6T copolymer, nylon 6T / 6I copolymer, nylon 66 / 6T / 6I, nylon 12/6
T, nylon 6T / M5T copolymer, nylon XD6
It is also practically preferable to use these nylon resins as a mixture according to other necessary properties such as moldability, heat resistance, and low water absorption.

The degree of polymerization of these polyamide resins is not particularly limited, and the relative viscosity measured at 25 ° C. in a 1% concentrated sulfuric acid solution is in the range of 1.5 to 5.0, especially 2.0 to 4.0. 0
Are preferred.

The liquid crystalline resin (B) of the present invention is a polymer capable of forming anisotropy when melted, and includes liquid crystalline polyester, liquid crystalline polyester amide, liquid crystalline polycarbonate, liquid crystalline polyester elastomer and the like.
Among them, those having an ester bond in the molecular chain are preferable, and liquid crystal polyesters and liquid crystal polyesteramides are particularly preferably used.

The liquid crystalline resin (B) which can be preferably used in the present invention is a liquid crystalline polyester containing a structural unit composed of p-hydroxybenzoic acid as an aromatic oxycarbonyl unit, and an ethylenedioxy unit as an essential component. Liquid crystalline polyester can also be preferably used. More preferred are polyesters consisting of the following structural units (I), (III) and (IV) or polyesters consisting of the structural units of (I), (II), (III) and (IV), the most preferred being ( I),
It is a polyester comprising the structural units of (II), (III) and (IV).

[0017]

Embedded image

(Where R ₁ in the formula is

[0019]

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R ₂ represents one or more groups selected from

[0021]

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And represents one or more groups selected from Also,
In the formula, X represents a hydrogen atom or a chlorine atom. Note that the sum of structural units (II) and (III) and structural unit (IV)
Are desirably substantially equimolar.

The structural unit (I) is a structural unit formed from p-hydroxybenzoic acid, and the structural unit (II) is 4,4
'-Dihydroxybiphenyl, 3,3', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7- Dihydroxynaphthalene,
Structural units formed from one or more aromatic dihydroxy compounds selected from 2,2-bis (4-hydroxyphenyl) propane and 4,4'-dihydroxydiphenyl ether, and structural unit (III) is a structure formed from ethylene glycol. Structural unit (IV) is terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid,
6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and 4,4'- The structural units generated from one or more aromatic dicarboxylic acids selected from diphenyl ether dicarboxylic acids are shown below. Of these, R ₁ is

[0024]

Embedded image

And R ₂ is

[0026]

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Is particularly preferred.

The above structural units (I), (II), (III) and (IV)
Is arbitrary. However, in order to exhibit the characteristics of the present invention, the following copolymerization amount is preferable.

That is, the structural units (I), (II) and (II)
I), in the case of a copolymer consisting of (IV), the structural unit (I)
The total of (II) and (II) is preferably from 30 to 95 mol%, more preferably from 40 to 93 mol%, based on the total of the structural units (I), (II) and (III). The structural unit (III) is the structural unit
It is preferably from 70 to 5 mol%, more preferably from 60 to 7 mol%, based on the total of (I), (II) and (III). The molar ratio [(I) / (II)] of the structural unit (I) to the structural unit (II) is preferably from 75/25 to 95/5, and more preferably from 78/22 to 93/7. . Further, it is preferable that the structural unit (IV) is substantially equimolar to the sum of the structural units (II) and (III).

On the other hand, when the above-mentioned structural unit (II) is not contained, the structural unit (I) should be 40 to 90 mol% with respect to the total of the structural units (I) and (III) from the viewpoint of fluidity. Is preferably 60 to 88 mol%, and the structural unit (IV) is preferably substantially equimolar to the structural unit (III).

As the liquid crystalline polyesteramide,
Polyesteramides that form an anisotropic molten phase containing p-iminophenoxy units formed from p-aminophenol in addition to the structural units (I) to (IV) are preferred.

The liquid crystalline polyester and the liquid crystalline polyester amide which can be preferably used include, in addition to the components constituting the structural units (I) to (IV), 3,3'-diphenyldicarboxylic acid and 2,2 ' -Aromatic dicarboxylic acids such as diphenyldicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, 3,4'- Dihydroxybiphenyl, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxybenzophenone, 3,4 '
-Aromatic diols such as dihydroxybiphenyl, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, and aliphatic and fats such as 1,4-cyclohexanedimethanol Cyclic diols, aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid, and p-aminobenzoic acid can be further copolymerized within a range that does not impair the liquid crystallinity.

The logarithmic viscosity of the liquid crystalline resin (B) used in the present invention can be measured in pentafluorophenol. At this time, 0.5 to 15.0 dl / g is preferable as a value measured at 60 ° C. at a concentration of 0.1 g / dl,
1.0 to 3.0 dl / g is particularly preferred.

The melt viscosity of the liquid crystalline resin (B) in the present invention is preferably 0.5 to 500 Pa · s, more preferably 1 to 2 Pa · s.
50 Pa · s is more preferred. In order to obtain a composition having better fluidity, the melt viscosity is preferably set to 50 Pa · s or less.

The melt viscosity is calculated as melting point (Tm) +10
It is a value measured by a Koka type flow tester under the condition of ° C and a shear rate of 1,000 (1 / second).

Here, the melting point (Tm) refers to an endothermic peak temperature (Tm) observed when a polymer that has been polymerized is measured from room temperature under a heating condition of 20 ° C./min.
After observation at m1), the temperature is maintained at a temperature of Tm1 + 20 ° C. for 5 minutes, cooled once to room temperature at a temperature lowering condition of 20 ° C./min, and then measured again at a temperature rising condition of 20 ° C./min. Endothermic peak temperature (Tm2).

The melting point of the liquid crystalline resin is not particularly limited, but is preferably 34 from the viewpoint of dispersibility in the polyamide resin.
The temperature is 0 ° C or lower, more preferably 330 ° C or lower.

The method for producing the liquid crystalline polyester used in the present invention is not particularly limited, and it can be produced according to a known polyester polycondensation method.

For example, in the production of the liquid crystalline polyester, the following production method is preferably mentioned. (1) p-acetoxybenzoic acid and diacylated aromatic dihydroxy compounds such as 4,4'-diacetoxybiphenyl and diacetoxybenzene and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid A method for producing a liquid crystalline polyester by a deacetic acid polycondensation reaction therefrom. (2) Reaction of aromatic dihydroxy compounds such as p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl and hydroquinone with aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid, and acetic anhydride. The phenolic hydroxyl group is acylated, and then a liquid crystalline polyester is produced by a deacetic acid polycondensation reaction. (3) Phenyl esters of p-hydroxybenzoic acid and aromatic dihydroxy compounds such as 4,4'-dihydroxybiphenyl and hydroquinone and diphenyl esters of aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid For producing liquid crystalline polyesters from polyphenols by a dephenol removal polycondensation reaction. (4) A predetermined amount of diphenyl carbonate is reacted with p-hydroxybenzoic acid and an aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, terephthalic acid, or isophthalic acid to form diphenyl esters, respectively.
A method in which an aromatic dihydroxy compound such as 4,4'-dihydroxybiphenyl or hydroquinone is added, and a liquid crystalline polyester is produced by a phenol-elimination polycondensation reaction. (5) In the presence of a bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid such as a polymer or oligomer of a polyester such as polyethylene terephthalate or an aromatic dicarboxylic acid such as bis (β-hydroxyethyl) terephthalate, the liquid crystal is prepared by the method of (1) or (2). A method for producing a conductive polyester.

Although the polycondensation reaction of the liquid crystalline polyester proceeds without a catalyst, metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, and metal magnesium can also be used.

The mixing ratio of the polyamide resin (A) and the liquid crystal resin (B) used in the present invention is 100
0.05 to 30 parts by weight of liquid crystal resin (B), preferably 0.1 to 25 parts by weight of liquid crystal resin (B), more preferably 1 to 20 parts by weight, relative to parts by weight. Parts by weight.

When the amount of the liquid crystalline resin (B) added is too small or too large with respect to the polyamide resin (A),
It is not preferable because a material having good mechanical properties such as good flow, thin-walled flame retardancy and impact resistance cannot be obtained.

For example, when the flame-retardant resin composition of the present invention requires further fluidity in a thin portion of a molded article, it is possible to add an acid anhydride. Examples of acid anhydrides include benzoic anhydride, isobutyric anhydride, itaconic anhydride, octanoic anhydride, glutaric anhydride, succinic anhydride, acetic anhydride, dimethylmaleic anhydride, decanoic anhydride, trimellitic anhydride, , 8-naphthalic acid, phthalic anhydride, maleic anhydride and the like.
8-Naphthalic acid, phthalic anhydride, maleic anhydride and the like are preferably used.

The amount of the acid anhydride used in the present invention is preferably from 0.01 to 5 parts by weight, more preferably from 0.1 to 5 parts by weight, based on 100 parts by weight of the polyamide resin from the viewpoint of the fluidity improving effect.
It is 0.5 to 3 parts by weight, particularly preferably 0.1 to 2 parts by weight. By using an acid anhydride, the flowability is improved and the range of molding conditions is widened. For example, in the case of a box-shaped product, it is possible to reduce the warpage due to the twist of the bottom surface. However, if the amount of the acid anhydride is too large, gas is generated at the time of compounding and molding, which results in poor biting, gas burning of the molded product and generation of voids. Also tend to decrease.

The state of the acid anhydride used in the present invention in the polyamide resin composition is not particularly limited, and any state of the acid anhydride, water or polyamide, a liquid crystal resin and a reaction product thereof with a monomer / oligomer can be used. It may be present at.

When the acid anhydride is blended with the flame-retardant resin composition of the present invention, it is not particularly limited, but it is usually preferable to perform melt-kneading, and a known method can be used for melt-kneading. For example, using a Banbury mixer, rubber roll machine, kneader, single screw or twin screw extruder, etc.
The composition can be melt-kneaded at a temperature of 80 to 380 ° C to obtain a composition. Preferably, an extruder is used, and the compounding order is not particularly limited. It is preferable that the polyamide resin (A) and the acid anhydride are kneaded at the same time. For example, the component (A) and the acid anhydride are blended, and then the liquid crystalline resin is mixed. (B) In the case of an extruder equipped with two-stage extrusion and a side feeder,
Pour from side or polyamide resin (A)
A method of simultaneously blending the components, the liquid crystalline resin (B) and the acid anhydride is preferably used.

The metal hydroxide (D) used in the present invention
Is at least one selected from Group II metal hydroxides and Group III metal hydroxides. Group II metals include magnesium, calcium, barium, zinc and the like, and Group III metals include aluminum and the like. Specific examples of preferred metal hydroxides include magnesium hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, aluminum hydroxide, and the like.
Particularly, magnesium hydroxide, aluminum hydroxide and the like are preferably used.

In the present invention, the amount of the metal hydroxide added is
Usually 0.1 to 30 parts by weight, based on 100 parts by weight of the resin composition (C) comprising the polyamide resin (A) and the liquid crystalline resin (B) (that is, the total of the components (A) and (B)).
Preferably 0.5 to 20 parts by weight, more preferably 1-1.
0 parts by weight. If the added amount of the metal hydroxide is too small, the effect of improving the flame retardancy is not sufficiently exhibited, and if it is too large, there is a tendency that physical properties such as a decrease in fluidity are reduced and the polymer itself acts as a decomposition accelerator.

The red phosphorus (E) used in the present invention is unstable as it is, and has the property of gradually dissolving in water or reacting with water gradually. What has been applied is preferably used. As a method for treating such red phosphorus, the method of pulverizing red phosphorus described in JP-A-5-229806 is not performed, and a red crushed surface having high reactivity with water and oxygen is not formed 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, a method of stabilizing by mixing with ε-caprolactam or trioxane, a method of mixing red phosphorus with phenolic, melamine, epoxy, or unsaturated polyester A method of stabilizing by coating with a thermosetting resin such as, for example, treating red phosphorus 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 surface of the red phosphorus. Method to stabilize, red phosphorus aluminum hydroxide, magnesium hydroxide, titanium hydroxide,
Examples include a method of coating with zinc hydroxide 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 grinding phosphorus, coating red phosphorus with thermosetting resin such as phenolic, melamine, epoxy, and unsaturated polyester A method in which red phosphorus is stabilized by coating it with aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide, etc., and particularly preferably, a crushed surface is formed on the red phosphorus surface. A method of forming red phosphorus into fine particles without forming the same, and converting red phosphorus into phenolic, melamine,
This is a method of stabilizing by coating with a thermosetting resin such as an epoxy-based or unsaturated polyester-based resin. Among these thermosetting resins, red phosphorus coated with a phenolic thermosetting resin or an epoxy thermosetting resin can be preferably used from the viewpoint of moisture resistance, and particularly preferably a phenolic thermosetting resin. Red phosphorus coated with resin.

The average particle size of red phosphorus before being blended 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.

The average particle diameter of red phosphorus used in the present invention is as described above. However, 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 or the like. The content of red phosphorus having a particle size of 75 μm or more is preferably 10% by weight or less, more preferably 8% by weight or less, particularly preferably 5% by weight or less from the viewpoints of flame retardancy, mechanical properties, wet heat resistance and recyclability. It is. The lower limit is not particularly limited, but is preferably as close to 0 as possible.

Here, the content of red phosphorus having a particle size of 75 μm or more contained in red phosphorus can be measured by classifying the particles using a 75 μm mesh. That is, 100 g of red phosphorus
From the residual amount Z (g) when classifying with a 5 μm mesh,
The content of red phosphorus having a particle size of 75 μm or more is (Z / 100) × 10
It can be calculated from 0 (%).

The conductivity of the red phosphorus 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 at 12 g).
Extraction treatment was performed at 1 ° C for 100 hours.
Measuring the conductivity of the extracted water diluted to 0 mL), the moisture resistance, mechanical strength, tracking resistance,
0.1 to 1000 μS from the viewpoint of recyclability
/ Cm, preferably 0.1-800 μS / cm,
More preferably, it is 0.1 to 500 μS / cm.

[0055] Commercial products of such preferred red phosphorus include "NOVA EXCEL" 140 and "NOVA EXCEL" F5 manufactured by Rin Kagaku Kogyo KK.

In the present invention, the amount of red phosphorus added is as follows: the resin composition (C) comprising the polyamide resin (A) and the liquid crystalline resin (B) (that is, the sum of the components (A) and (B)).
Usually 0.01 to 30 parts by weight, preferably 0.05 to 20 parts by weight, more preferably 0.06 to 100 parts by weight with respect to 00 parts by weight.
It is 10 parts by weight, more preferably 0.08 to 8 parts by weight. If the amount of added red phosphorus is too small, the effect of improving the flame retardancy is not sufficiently exhibited, while if it is too large, the physical properties are reduced and the composition tends to work as a combustion accelerator contrary to the flame retardant effect.

The flame-retardant resin composition of the present invention is further added with a metal oxide as a stabilizer for red phosphorus to improve the stability and strength during extrusion and molding, heat resistance, terminal corrosion of molded articles, and the like. Can be improved. Specific examples of such a metal oxide include cadmium oxide, zinc oxide, cuprous oxide, cupric oxide, ferrous oxide, ferric oxide, cobalt oxide, manganese oxide, molybdenum oxide, tin oxide and Titanium oxide and the like can be mentioned, among which cadmium oxide, cuprous oxide, cupric oxide, metal oxides other than Group I and / or II metals such as titanium oxide are preferable, and particularly cuprous oxide, Cupric oxide and titanium oxide are preferred, but may be Group I and / or II metal oxides. Titanium oxide is most preferable in order to further improve non-coloring properties in addition to stability and strength during extrusion and molding, heat resistance, and terminal corrosion of molded articles.

The addition amount of the metal oxide is determined from the viewpoint of mechanical properties and moldability from the viewpoint of mechanical properties and moldability. The resin composition (C) comprising the polyamide resin (A) and the liquid crystal resin (B) (that is, the component (A)
The amount 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 total components.

When the flame-retardant resin composition of the present invention is further added with a fluorine-based resin, the drop (drip) of droplets during combustion is suppressed. Examples of such fluororesins include polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, and (tetrafluoroethylene / Ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / ethylene) copolymer and the like. Among them, polytetrafluoroethylene, (tetrafluoroethylene / (Perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer, and polyvinylidene fluoride are preferred. Polytetrafluoroethylene, (tetrafluoroethylene / ethylene) copolymer are preferable.

The addition amount of the fluorine-based resin is determined from the viewpoint of mechanical properties and moldability from the viewpoint of mechanical properties and moldability. The total amount is usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight with respect to 100 parts by weight.

In the present invention, it is possible to use a filler to impart mechanical strength and other properties to the flame-retardant resin composition, and it is not particularly limited, but fibrous, plate-like, powdery Non-fibrous fillers such as particles and granules can be used. Specifically, for example, glass fiber, PA
N-based or pitch-based carbon fiber, stainless fiber, metal fiber such as aluminum fiber or brass fiber, organic fiber such as aromatic polyamide fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, oxidation Titanium fiber, silicon carbide fiber, rock wool,
Fibrous such as potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, whisker-like filler, mica, talc, kaolin, silica, calcium carbonate, glass beads, glass flake, glass micro balloon, clay, Molybdenum disulfide, wollastenite, titanium oxide,
A powdery, granular or plate-like filler such as zinc oxide, calcium polyphosphate, graphite and the like can be used. Among the fillers, glass fibers and PAN-based carbon fibers are preferably used. The type of the glass fiber is not particularly limited as long as it is generally used for reinforcing a resin. For example, a long fiber type or a short fiber type chopped strand, a milled fiber or the like can be used. Further, two or more of the above fillers can be used in combination. The filler used in the present invention may be used after its surface is treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, or the like) or another surface treatment agent. .

Further, the glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.

The amount of the filler to be added is 10% for the resin composition (C) comprising the polyamide resin (A) and the liquid crystal resin (B) (that is, the sum of the components (A) and (B)).
The amount is 0.5 to 300 parts by weight, preferably 10 to 250 parts by weight, more preferably 20 to 150 parts by weight with respect to 0 parts by weight.

Further, the flame-retardant resin composition of the present invention comprises
Antioxidants and heat stabilizers (such as hindered phenols, hydroquinones, phosphites and their substitutes), ultraviolet absorbers (such as resorcinol,
Coloring agents, such as salicylates, benzotriazoles, benzophenones), phosphites, hypophosphites, etc., lubricants, dyes (eg, nigrosine) and pigments (eg, cadmium sulfide, phthalocyanine, etc.), lubricants and the like. Release agents (montanic acid and its salts, its esters, its half esters, stearyl alcohol, stearamide and polyethylene wax, etc.),
One or more metal hydroxides selected from carbon black as a conductive agent or coloring agent, a crystal nucleating agent, a plasticizer, and a flame retardant selected from red phosphorus and a hydroxide of a group II metal and a hydroxide of a group III metal. , But other flame retardants (eg, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, melamine and cyanuric acid or a salt thereof), flame retardant aids, slidability improvers (such as graphite) ) And ordinary additives such as an antistatic agent can be added to further impart predetermined characteristics.

Further, according to the necessity of further property improvement, an acid-modified olefin polymer such as maleic anhydride, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / non-conjugated diene may be used. Copolymer, ethylene / ethyl acrylate copolymer, ethylene /
Glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer and ethylene /
A propylene-g-maleic anhydride copolymer, an olefinic copolymer such as ABS, a polyester polyether elastomer, a polyester polyester elastomer, and one or more mixtures selected from elastomers are added to obtain predetermined characteristics. It can be further provided.

The flame-retardant resin composition of the present invention is produced by a generally known method. For example, extruders with or without premixing of polyamide resin (A) and liquid crystalline resin (B), metal hydroxide (D) and red phosphorus (E) with other necessary additives and fillers It is prepared by sufficiently melting and kneading the mixture, and preferably from the viewpoint of handleability and productivity, a part of the resin component to be finally compounded, specifically, one of the components (A) Part or all,
A part or all of the component (B), or a part of the components (A) and (B) finally contained, and the metal hydroxide (D) and / or red phosphorus (E) are once melt-kneaded and then actually mixed. Resin composition (M) having a higher concentration than the amount of metal hydroxide and / or red phosphorus to be blended with the flame retardant resin composition
And a resin composition (M) having a high concentration of a metal hydroxide (D) and / or red phosphorus (E) in the remaining components of the polyamide resin (A) or the liquid crystal resin (B) and other components. It is prepared by melt-kneading optional additives and fillers.

Alternatively, a part of the resin component to be finally blended (specifically, the same as described above), metal hydroxide (D) and / or red phosphorus (E), and other optional additives can be used. Once the agent is melt-kneaded, the metal hydroxide (D) to be actually blended with the flame-retardant resin composition and / or
Or a resin composition (M) having a higher concentration than the amount of red phosphorus (E)
And the remaining components of the polyamide resin (A) or the liquid crystal resin (B) and the metal hydroxide (D) and / or
Alternatively, it is prepared by melt-kneading additives and fillers other than the optional additives added during the production of the resin composition (M) having a high concentration of red phosphorus (E).

As described above, a resin composition (M) having a higher concentration than the amounts of the metal hydroxide (D) and / or red phosphorus (E) to be actually incorporated into the flame-retardant resin composition is produced. When other optional additives are blended at the stage, it is preferable that these optional additives are previously mixed with the metal hydroxide and / or red phosphorus.

Among the additives that can be used arbitrarily, when a metal oxide used as a stabilizer for red phosphorus, particularly titanium oxide, is added, the titanium oxide produces a high-concentration product (M) of red phosphorus. When red phosphorus and titanium oxide are mixed in advance using a mechanical mixing device such as a Henschel mixer, the stability of red phosphorus, the dispersibility of red phosphorus, and the obtained resin The non-coloring property of the composition can be improved.

The high-concentration product (M) of the metal hydroxide (D) and / or red phosphorus (E) includes (1) a metal hydroxide and / or red phosphorus containing the polyamide resin (A) as a resin component. (2) High concentration of metal hydroxide (D) and / or red phosphorus (E) containing liquid crystalline resin (B) as a resin component, (3) Polyamide resin (A) and liquid crystalline Both of the metal hydroxide (D) containing the resin (B) as a resin component and / or the high-concentration product of red phosphorus (E) exhibit this effect. Preferably, a metal hydroxide (D) containing a liquid crystalline resin (B) as a resin component and a high-concentration product of red phosphorus (E) are used as the metal hydroxide (D) in the flame-retardant resin composition. ) And red phosphorus (E) are improved, and the metal hydroxide (D)
Also functions as a stabilizer for red phosphorus (E), so that thin-walled flame retardancy, heat stability, etc. are improved.

The content of the metal hydroxide (D) and / or red phosphorus (E) in such a high-concentration product (M) of the metal hydroxide (D) and / or red phosphorus (E) is determined by the amount of the metal hydroxide (D) In terms of manufacturability in the production of high-concentration products of oxide (D) and / or red phosphorus (E), dispersibility of metal hydroxide (D) and red phosphorus (E), and finally obtained In view of the flame retardancy, mechanical properties, moldability, and heat resistance of the resin composition, 0.5 to 300 parts by weight based on 100 parts by weight of the resin component (total of the polyamide resin (A) and the liquid crystal resin (B)). Parts by weight, more preferably 1 to 250 parts by weight, more preferably 5 to 2 parts by weight.
00 parts by weight.

The resin composition having a high red phosphorus concentration (M)
Is preferably used in the form of a so-called master pellet, but is not limited thereto, and may be in the form of a chip, a powder, or a mixture thereof. The polyamide resin (A) and the liquid crystalline resin (B) mixed with the component (M) are preferably in the form of pellets, but are not limited thereto, and are not limited to so-called chips, powders, or chips and powders. It may be a mixture,
Forms of polyamide resin (A) and liquid crystalline resin (B),
It is preferable that the sizes and shapes are substantially the same or similar to each other, since they can be uniformly mixed. In producing the resin composition, the composition is melt-kneaded at 180 to 350 ° C. using, for example, a single-screw extruder equipped with a “Unimelt” type screw, a twin-screw extruder, a tri-screw extruder, and a kneader-type kneader. Things.

The flame-retardant resin composition thus obtained has fluidity, thin-walled flame retardancy and impact resistance, heat stability, slidability,
It is a composition with improved surface appearance and metal corrosion resistance,
Particularly in the case of thin-walled flame retardancy, in many cases, it is possible to achieve UL-94 standard V-0 flame retardancy even with a thickness of 0.8 mm.

Further, the molding method for molding the molded article is a conventional molding method (injection molding, extrusion molding, blow molding, press molding, injection press molding, etc.), and is applied to a three-dimensional molded article, sheet, container pipe or the like. It can be processed, and it can be preferably applied to molded articles having a thin portion (for example, a plate-shaped molded article or a box-shaped molded article), particularly molded articles having a thin-walled portion of 1.0 mm or less, by taking advantage of its excellent fluidity. . Specifically, a molded article having a portion having a thickness of 1.0 mm or less with respect to the total surface area of the molded article of 10% or more, more preferably a molded article having a portion of 1.0 mm or less with 15% or more, still more preferably It is effective for a molded article having a portion of 0.8 mm or less of 10% or more. As a molding method, injection molding or injection press molding is preferred. Further, the flame-retardant resin composition of the present invention can be molded by a generally known method, and can be formed into molded articles of any shape such as injection molding, extrusion molding, compression molding, etc., sheets and films. it can. Among them, it is particularly suitable for use in injection molded products, and is suitable for various mechanical mechanism parts, electric and electronic parts, or automobile parts.

Further, the flame-retardant resin composition of the present invention can reduce defects such as unfilled, deformed and cracked due to insufficient fluidity when obtaining molded articles requiring fluidity and thin-walled flame retardancy. Yes, and in the case of obtaining a large size, decomposition of the polymer can be suppressed even if it stays in the cylinder of the molding machine, and the obtained molded product has good flame retardancy and impact resistance, slidability, surface appearance, In addition, when used for a housing, a connector, or the like, the corrosion of adjacent metal terminals and the like is improved, so that a highly reliable molded product can be obtained.

The flame-retardant resin composition of the present invention also includes various gears, various cases, sensors, LED lamps, connectors, sockets, paper separating claws, resistors, relay cases,
Switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, LCD / display parts, FDD carriages, FDD chassis, HDD parts, motor / brush holders, parabolic antennas, electric / electronic parts such as computer-related parts; VTR parts, TV parts, irons,
Home and office represented by hair dryers, rice cooker parts, microwave parts, audio parts, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. Electrical product parts, office computer related parts, telephone related parts, facsimile related parts, copier related parts, washing jigs, oilless bearings, stern bearings, underwater bearings, etc., various bearings, motor parts, lighters, typewriters, etc. , Optical equipment such as microscopes, binoculars, cameras, watches, etc., precision machinery-related parts, alternator terminals, alternator connectors, IC regulators, potentiometer bases for light drier, exhaust gas valves, etc. Seed valves, fuel-related / exhaust / intake pipes, 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, throttle Position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dust tribute Starter switch, starter relay, transmission wire harness,
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 automotive and vehicle related parts such as lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, power seat gear housing, ignition coil parts, and various other uses. In particular, housings for various cases, such as various cases, switches, bobbins, connectors, socket connectors, housings for mobile telephone housings, personal computer housings, etc., having a thin portion of 1.0% or less of 10% or more of the entire molded article ( Particularly useful as a housing).

[0077]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the gist of the present invention is not limited to the following Examples.

Reference Example 1 Production of polyamide resin <A-1> Amilan CM3001 which is polyamide 66
N (manufactured by Toray Industries, Inc.) was used.

<A-2> Amilan C which is polyamide 6
M1010 (manufactured by Toray Industries, Inc.) was used.

<A-3> As the polyamide 66 copolymer, the following polyamide copolymer was produced.

A mixed aqueous solution (solid raw material concentration: 60% by weight) of 30 mol% of hexamethylene diammonium terephthalate (6T salt) and 70 mol% of hexamethylene diammonium adipate (AH salt) is charged into a pressure polymerization vessel and stirred. After raising the temperature and reacting at a steam pressure of 19 kg / cm ² for 1.5 hours, the pressure was gradually released over about 2 hours, and further reacted under normal pressure nitrogen stream for about 30 minutes to obtain a relative viscosity of 2.63 (in sulfuric acid). ), Melting point 2
A polyamide 6T / 66 at 78 ° C. was obtained.

Reference Example 2 Method for producing liquid crystalline resin <LCP1> 528 parts by weight of p-hydroxybenzoic acid,
126 parts by weight of 4,4'-dihydroxybiphenyl, 112 parts by weight of terephthalic acid, 864 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 586 parts by weight of acetic anhydride were equipped with a stirring blade and a distilling tube. The reaction vessel was charged and polymerization was carried out. Aromatic oxycarbonyl unit 42.
5 mol%, aromatic dioxy unit 7.5 mol%, ethylenedioxy unit 50 mol%, aromatic dicarboxylic acid unit 5
Melting point consisting of 7.5 mol% 208 ° C., 15 Pa · s (218
° C, orifice 0.5φ × 10mm, shear rate 1,000
(1 / sec)).

Each evaluation was performed according to the following method.

(1) Fluidity Using the following molding machine, an injection speed of 99% and an injection pressure of 500 were used.
0.8mm thickness × 100mm under the conditions of kgf / cm ²
The flowability (flow length) was measured using a square test piece (width) × 150 mm (length).

(2) Impact resistance 1/8 according to ASTM D256 using the following molding machine
The inch Izod impact value was measured.

(3) Thermal stability Using a molding machine described below, a bending test piece was obtained at the cylinder temperature shown in Table 1 and tested under the conditions of ASTM D790, and the amount of bending deflection was measured (the amount of deflection without stagnation). The amount of flexure was measured under the same conditions except that the material was retained in the cylinder for 10 minutes (the amount of flexure with retention). The retention rate of the deflection amount (deflection retention rate) (%) was calculated as (deflection amount with retention / deflection amount without retention) × 100 (%).

(4) Metal Corrosion Resistance 1/8 inch Iz at the temperature shown in Table 1 using the following molding machine
An od specimen was prepared and 0.5 g between two Izod impact specimens
mm thick copper plate, and put in an oven at 150 ° C for 100
After the treatment, the copper plate was observed for corrosion. Evaluation,
○: No corrosion, ×: Corrosion.

(5) Slidability A rectangular plate having a length of 30 mm, a width of 30 mm and a thickness of 3 mm was formed using the molding machine described below, and the square plate was fixed to a jig, and a load of 3 kg was applied to 18 mmφ × 2 mm in thickness. Press the cylindrical aluminum to the center of the square plate and apply
After rotating for 1 hour at 5 rpm, the amount of wear was measured.

(6) Flame Retardancy In accordance with the UL-94 standard, a 0.8 mm thick test piece was evaluated for flame retardancy.

(7) Rigidity A molded product having a thickness of 127 mm × 12.7 mm × 3.2 mm was molded using the following molding machine, and the flexural modulus was measured in accordance with ASTM D790.

(8) Warping (twisting property) Four-point gate 40 mm long × 100 mm wide × 10 mm high
When a box-shaped molded product having a thickness of 1 mm was molded using the following molding machine at a minimum filling pressure of +0.5 MPa, the warpage of the bottom surface was evaluated. The evaluation was ○: no warpage, Δ: slight, ×: large warpage.

Examples 1 to 6 and Comparative Examples 1 to 6 Magnesium hydroxide and red phosphorus (Nova Excel 140) were dry-blended with 100 parts by weight of LCP1 and 20 parts by weight of red phosphorus (Nova Excel 140), respectively. The mixture was melt-kneaded at + 15 ° C. of the melting point of the liquid crystalline polyester to obtain pellets of a high concentration product (M1). A pellet of a high concentration product (M2) produced in the same manner as in M1 except that aluminum hydroxide was used instead of magnesium hydroxide was obtained.

Next, a polyamide resin and a liquid crystalline polyester, glass fiber (9 μm diameter, 3 mm length) and PAN-based carbon fiber (6 mm
Long) and high-concentration products (M1 or M2) or red phosphorus were dry-blended and melt-kneaded at a cylinder temperature shown in Table 1 using a 30 mmφ twin screw extruder to form pellets. The pellets are supplied to a Toshiba IS55EPN injection molding machine (manufactured by Toshiba Machine Co., Ltd.), and a test piece is formed at a cylinder temperature shown in Table 1 and a mold temperature of 80 ° C. by a method for each evaluation item. did.

Examples 7 and 8 The same evaluation as in Examples 2 and 6 was carried out by further adding succinic anhydride as an acid anhydride in the amount shown in Table 2.

The addition method was as follows: using a twin screw extruder with a side feeder, a polyamide resin and an acid anhydride were originally added at the temperature shown in Table 2, a filler and a highly concentrated product were added from a side feeder, and the composition pellets were added. Obtained. Next, the pellets were supplied to a Toshiba IS55EPN injection molding machine (manufactured by Toshiba Machine Co., Ltd.), and the test pieces were prepared by the method for each evaluation item under the conditions of the cylinder temperature shown in Table 2 and the mold temperature of 80 ° C. Molded.

As is clear from Table 1, the composition of the present invention is superior in flowability, thin-walled flame retardancy and retention stability as compared with Comparative Examples, and the obtained molded product has impact resistance. The sliding properties and the metal corrosion resistance are good, and the use of an acid anhydride improves the rigidity and the warp deformability of the molded product, as is clear from Table 2. It can be seen that the method is very excellent when obtaining molded articles such as.

[0097]

[Table 1]

[0098]

The thermoplastic resin composition of the present invention has excellent fluidity, thin-walled flame retardancy and impact resistance, thermal stability, slidability, surface appearance, metal corrosion resistance, rigidity and molded products. Since the warp deformation property is improved, it is a material suitable for electric / electronic-related equipment, precision equipment-related equipment, office equipment, automobile, and other various applications requiring these properties.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 67:03)

Claims (9)

[Claims] 1. A Group II metal hydroxide based on 100 parts by weight of a resin composition (C) comprising 100 parts by weight of a polyamide resin (A) and 0.05 to 30 parts by weight of a liquid crystalline resin (B). Flame retardant containing 0.1 to 30 parts by weight of one or more metal hydroxides (D) selected from hydroxides of Group III and III metals and 0.01 to 30 parts by weight of red phosphorus (E) Resin composition. 2. The red phosphorus has a conductivity of 0.1 to 1000 μS / c.
The flame-retardant resin composition according to claim 1, wherein m is m. 3. The flame-retardant resin composition according to claim 1, further comprising 0.5 to 300 parts by weight of a filler based on 100 parts by weight of the resin composition (C). 4. The flame-retardant resin composition according to claim 1, wherein the liquid crystalline resin (B) contains an ethylenedioxy unit. 5. The flame-retardant resin composition according to claim 1, wherein the metal hydroxide (D) is at least one selected from magnesium hydroxide, calcium hydroxide and aluminum hydroxide. 6. The flame-retardant resin composition according to claim 1, which has a flame retardancy of V-0 at a thickness of 0.8 mm according to UL-94 standard. 7. The amount of the metal hydroxide to be actually blended into the flame-retardant resin composition by temporarily melting and kneading a part of the resin component to be finally blended and the metal hydroxide and / or red phosphorus. And / or producing a resin composition having a concentration higher than the amount of red phosphorus, and then producing the flame-retardant resin composition according to any one of claims 1 to 6. Method. 8. A molded article comprising the flame-retardant resin composition according to any one of claims 1 to 6, wherein the molded article is a mechanical mechanism part, an electric / electronic part or an automobile part. . 9. A molded article comprising the flame-retardant resin composition according to any one of claims 1 to 6, wherein the molded article is a thin plate having a plate shape or a box shape and a thickness of 1.0 mm or less. A molded article characterized by having at least 10% of the total surface area of the molded article.