JP2000109687A - Flame-retardant resin composition and molded item thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin compsn. improved in flowability, thin-wall flame retardance, hydrolysis resistance, surface appearance, metal- corroding properties, and resistance to warping by incorporating a specified amt. of red phosphorus into a resin compsn. (D) comprising a polyamide resin (A), a liq. crystalline resin (B), and a thermoplastic polyester resin (C). SOLUTION: 0.01-30 pts.wt. red phosphorus having a conductivity of 0.1-1,000 μS is incorporated into 100 pts.wt. compsn. prepd. from 100 pts.wt. ingredient A, 1-50 pts.wt. ingredient B, and 0.1-50 pts.wt. ingredient C. Examples of ingredient A is nylon 6 and nylon 66. Though ingredient A is not specifically limited in degree of polymn., one having a relative viscosity of 1.5-5.0 is used. Liq. crystalline polyesters and liq. crystalline polyesteramides are examples of ingredient B. Ingredient C having a logarithmic viscosity of 0.2-3.0 dl/g is pref. Red phosphorus coated with a thermosetting phenol resin and having an average particfle size of 35-0.01 μm is pref.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition having improved fluidity, thin-walled flame retardancy and hydrolysis resistance, surface appearance, metal corrosion, warpage, and a molded article thereof. It is.

[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-mentioned problems, and provides fluidity, thin-walled flame retardancy and hydrolysis resistance, surface appearance, metal corrosion,
An object of the present invention is to obtain a flame-retardant resin composition having improved warp deformability and 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 provides (1) a resin composition comprising 100 parts by weight of a polyamide resin (A), 0.1 to 50 parts by weight of a liquid crystalline resin (B), and 0.1 to 50 parts by weight of a thermoplastic polyester resin (C). (D) Red phosphorus 0.01 to 100 parts by weight
(2) The flame-retardant resin composition according to the above (1), wherein the red phosphorus has a conductivity of 0.1 to 1000 μS / cm. 3) a reinforced flame-retardant resin composition further comprising 0.5 to 300 parts by weight of a filler in 100 parts by weight of the resin composition (D);
(4) The flame-retardant resin composition according to any one of the above (1) to (3), wherein the liquid crystalline resin (B) contains an ethylenedioxy unit;
(1) a flame-retardant resin composition according to any one of the above (1) to (4), which has a flame retardancy of -0; After preparing a resin composition having a higher red phosphorus concentration than the amount of red phosphorus to be actually blended in the thermoplastic resin composition, the flame-retardant resin composition according to any one of the above (1) to (5) (7) The method for producing a flame-retardant resin composition, wherein
(5) A molded article comprising the flame-retardant resin composition according to any of (5), wherein the molded article is a mechanical mechanism part, an electric / electronic part or an automobile part. )
A molded article comprising the flame-retardant resin composition according to any one of (1) to (5), wherein the molded article is a plate-shaped or box-shaped thin part having a thickness of 1.0 mm or less. To provide a molded article characterized by having 10% or more.

[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 9T, nylon 6T / 6 copolymer, nylon 66 / 6T copolymer, nylon 6
Examples include T / 6I copolymer, nylon 66 / 6T / 6I, nylon 12 / 6T, nylon 6T / M5T copolymer and the like. Further, these nylon resins may be used in combination with other materials such as moldability, heat resistance, and low water absorption. It is also practically suitable to use it as a mixture depending on the required characteristics.

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]

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(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)] between the structural units (I) and (II) is preferably 75.
/ 25 to 95/5, more preferably 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. Refers to the endothermic peak temperature (Tm2).

The melting point of the liquid crystalline resin is not particularly limited, but is preferably 340 from the viewpoint of dispersibility in the thermoplastic resin.
° 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 crystal 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 thermoplastic polyester (C) used in the present invention is a non-woven fabric obtained by a condensation reaction containing a dicarboxylic acid (or an ester-forming derivative thereof) and a diol (or an ester-forming derivative thereof) as main components. It is a liquid crystal polymer or copolymer, or a mixture thereof. Alternatively, it is an aromatic homo- or co-polycarbonate resin obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester.

Specifically, the dicarboxylic acid component includes terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid Acid, 4,4′-diphenyl ether dicarboxylic acid, aromatic dicarboxylic acid such as 5-sodium sulfoisophthalic acid, adipic acid, sebacic acid, azelaic acid, aliphatic dicarboxylic acid such as dodecanedioic acid,
Alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and ester-forming derivatives thereof; The diol component has 2 to 20 carbon atoms.
Aliphatic glycols, ie, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6
-Hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, etc.
Alternatively, long-chain glycols having a molecular weight of 400 to 6000, that is, polymethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, and the like, and ester-forming derivatives thereof may be used.

Preferred examples of these polymers or copolymers include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycyclohexylene dimethylene terephthalate and polyethylene-1,2-bis ( Phenoxy) ethane-4,
In addition to 4'-dicarboxylate, polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / adipate, polybutylene terephthalate / sebacate, polybutylene terephthalate / decane dicarboxylate, polyethylene terephthalate / adipate, polyethylene Terephthalate / 5-sodium sulfoisophthalate, polybutylene terephthalate / 5-sodium sulfoisophthalate, etc., such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate,
Polybutylene naphthalate, polycyclohexylene dimethylene terephthalate, polybutylene terephthalate /
Adipate, polybutylene terephthalate / decane dicarboxylate, polyethylene terephthalate / adipate and the like are particularly preferred, and polyethylene terephthalate is most preferred.

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

Among these thermoplastic polyesters, the aromatic homo or copolycarbonate resin has a logarithmic viscosity of 0.2 to 3.0 dl / g measured at 20 ° C. at a concentration of 1.0 g / dl in methylene chloride. , Especially 0.3 ~
Those having a range of 1.5 dl / g are preferably used. Other than that, those having an intrinsic viscosity of 0.36 to 1.60 dl / g, particularly 0.52 to 1.35 dl / g when the o-chlorophenol solution is measured at 25 ° C. have mechanical properties, It is suitable from the viewpoint of moldability. If the intrinsic viscosity is too low, mechanical properties tend to be poor, and if the intrinsic viscosity is too high, moldability tends to be poor.

The method for producing the polyester resin composition used in the present invention can be carried out by a known method.

The polyamide resin (A), liquid crystal resin (B) and thermoplastic polyester resin (C) used in the present invention
The compounding ratio of (B) is 0.1 to 50 parts by weight, (C) 0.1 to 50 parts by weight, preferably (B) 0.5 to 40 parts by weight, and (C) is 100 parts by weight of the polyamide resin. ) 1
45 parts by weight, more preferably (B) 1 to 35 parts by weight,
(C) 5 to 40 parts by weight.

In the present invention, one of the important points is a delicate balance of each of the components (A), (B) and (C), and the addition amount of (B) and (C) is too small or too large. In such a case, a material having good mechanical properties such as good fluidity, thin-walled flame retardancy, and hydrolysis resistance cannot be obtained, which is not preferable.

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 0.01 to 5 parts by weight, more preferably 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, when the amount of the acid anhydride is too large, gas is generated at the time of compounding and molding, causing poor biting, gas burning of the molded product and generation of voids, and the obtained molded product has not only a surface appearance but also mechanical properties. It tends 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 usually it is 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), the acid anhydride, and the polyester resin (C) are mixed. In the case of an extruder equipped with two-stage extrusion and a side feeder, the liquid crystalline resin (B) is charged from the side or
Alternatively, a polyamide resin (A) component, a polyester resin (C) component and an acid anhydride are blended, and then, in the case of an extruder equipped with a two-stage extruder and a side feeder, a liquid crystal resin (B) component is charged from the side, A method of simultaneously blending the polyamide resin (A) component, the liquid crystalline resin (B), the polyester resin (C), and the acid anhydride is preferably used.

The red phosphorus used in the present invention is unstable as it is, and has the property of gradually dissolving in water or reacting gradually with water. 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 stabilizing by coating red phosphorus with a thermosetting resin such as a phenol-based, melamine-based, epoxy-based, unsaturated polyester-based, A method in which red phosphorus is treated with an aqueous solution of a metal salt such as copper, nickel, silver, iron, aluminum and titanium to precipitate and stabilize a metal phosphorus compound on the red phosphorus surface. Coating with luminium, magnesium hydroxide, titanium hydroxide, zinc hydroxide, etc., stabilizing by coating the surface of red phosphorus with iron, cobalt, nickel, manganese, tin, etc. by electroless plating and combining them Examples of the method include, but are not limited to, a method of pulverizing red phosphorus without pulverizing the red phosphorus and forming a crushed surface on the surface of the red phosphorus; a method of converting the red phosphorus into a phenol-based, melamine-based, epoxy-based, and unsaturated A method of stabilizing by coating with a thermosetting resin such as a polyester-based resin, converting red phosphorus to aluminum hydroxide,
It is a method of stabilizing by coating with magnesium hydroxide, titanium hydroxide, zinc hydroxide, etc., and particularly preferred is a method of forming red phosphorus into fine particles without forming a crushed surface on the surface of red phosphorus. This is a method of stabilizing by coating with a thermosetting resin such as a phenol-based, melamine-based, epoxy-based, and 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, moisture and 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 size of red phosphorus used in the present invention is as described above. However, red phosphorus having a large particle size contained in red phosphorus, that is, red phosphorus having a particle size 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 diameter of 75 μm or more contained in the red phosphorus can be measured by classification 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 (the conductivity is determined by adding 100 mL of pure water to 5 g of red phosphorus, and adding, for example,
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.

[0059] 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 determined by the resin composition (D) comprising the polyamide resin (A), the liquid crystal resin (B) and the thermoplastic polyester resin (C) (ie, (A), (B) , (C) component) 100 parts by weight, usually 0.01 to 30 parts by weight, preferably 0.05 to 30 parts by weight.
20 parts by weight, more preferably 0.06 to 10 parts by weight, even more preferably 0.08 to 5 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 further comprises a metal oxide as a stabilizer for red phosphorus to improve the stability and strength during extrusion and molding, heat resistance, and terminal corrosion of molded articles. 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 amount of the metal oxide added is 100 parts by weight of the resin composition (D) composed of the polyamide resin (A), the liquid crystal resin (B) and the thermoplastic polyester resin (C) from the viewpoint of mechanical properties and moldability. The amount is preferably 0.01 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight.

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 amount of the fluororesin added is 100 parts by weight of the resin composition (D) comprising the polyamide resin (A), the liquid crystal resin (B) and the thermoplastic polyester resin (C) from the viewpoint of mechanical properties and moldability. It 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.

In the present invention, it is possible to use a filler to impart mechanical strength and other properties to the flame-retardant resin composition. 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. .

The glass fibers may be covered 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 is determined by the resin composition (D) comprising the polyamide resin (A), the liquid crystal resin (B) and the thermoplastic polyester resin (C) (ie, (A), (B) and (B)). 0.5 to 300 parts by weight, preferably 10 to 300 parts by weight, per 100 parts by weight of component (C)).
It is 250 parts by weight, more preferably 20 to 150 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.),
Carbon black as a conductive agent or a coloring agent, a crystal nucleating agent, a plasticizer, and red phosphorus as a flame retardant are preferably used, but other flame retardants (eg, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, magnesium hydroxide, Ordinary additives such as melamine and cyanuric acid or a salt thereof, a flame retardant aid, a slidability improver (such as graphite), and an antistatic agent can be added to further impart predetermined characteristics.

Further, according to the necessity of further property improvement, acid-modified olefin polymers such as maleic anhydride, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / non-conjugated diene 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 usually produced by a known method. For example, polyamide resin (A), liquid crystal resin (B) and thermoplastic polyester resin (C)
Is prepared by pre-mixing red phosphorus and other necessary additives and fillers with or without an extruder and melting and kneading them sufficiently. In view of the above, a part of resin components to be finally blended, specifically, one or more selected from polyamide resin (A), liquid crystal resin (B), and thermoplastic polyester resin (C) (For example, part or all of (A), part or all of component (B), part or all of component (C), part or all of components (A) and (B), (A) and (C) a part or all of the components, or (B) and (C) a part or all of the components) or finally contained (A),
A resin composition (E) having a higher red phosphorus concentration than the amount of red phosphorus to be actually blended into the flame retardant resin composition by melt-kneading a part of the components (B) and (C) and red phosphorus once. The resin composition (E) having a high red phosphorus concentration and any other additives that can be produced and added to the remaining polyamide resin (A), liquid crystal resin (B), or thermoplastic polyester resin (C) components. It is prepared by melt-kneading the agent and the filler.

Alternatively, a part of the resin component to be finally blended (specifically, the same as above), red phosphorus and other optional additives can be melt-kneaded once and then actually flame-retarded. A resin composition (E) having a red phosphorus concentration higher than the amount of red phosphorus to be blended in the resin composition is produced, and the remaining polyamide resin (A), liquid crystal resin (B), or thermoplastic polyester resin (C) And a filler other than the optionally used additive and the filler added at the stage of the resin composition (E) having a high red phosphorus concentration in the component (A) and the component (A) are melt-kneaded.

At the stage of producing the resin composition (E) having a higher red phosphorus concentration than the amount of red phosphorus to be actually incorporated into the flame-retardant resin composition as described above, it can be used arbitrarily. When the additives are blended, it is preferable that these optional additives are mixed with red phosphorus in advance.

Among the additives which 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 (E) 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 content of red phosphorus in the high-red-phosphorus-concentration product (E) depends on the production of the high-concentration red-phosphorus product, the dispersibility of red phosphorus, and the difficulty of the flame-retardant resin composition finally obtained. From the viewpoints of flammability, mechanical properties, and moldability, the resin component (total of the polyamide resin (A), the liquid crystal resin (B), and the thermoplastic polyester resin (C)) is 100 parts by weight to 5 to 300 parts by weight.
It is preferably 25 parts by weight, particularly preferably 25 to 200 parts by weight.

The red phosphorus high concentration product (E) includes (1) a high red phosphorus concentration product consisting only of the polyamide resin (A), (2) a high red phosphorus concentration product consisting only of the liquid crystal resin (B), 3) Red phosphorus high concentration product consisting of thermoplastic polyester resin (C) only, (4) Red phosphorus high concentration product consisting of polyamide resin (A) and liquid crystalline resin (B), (5) Polyamide resin (A) and Red phosphorus high concentration product comprising thermoplastic polyester resin (C), (6) Red phosphorus high concentration product comprising liquid crystalline resin (B) and thermoplastic polyester resin (C), (7)
Any of the high-concentration red phosphorus products composed of the polyamide resin (A), the liquid crystal resin (B), and the thermoplastic polyester resin (C) exhibit the effect. Preferably a liquid crystalline resin (B)
Using only a high-concentration product of red phosphorus consisting only of the thermoplastic polyester resin (C), the dispersibility of red phosphorus in the flame-retardant resin composition is high, and the thin-walled flame retardancy and heat resistance are improved. I do.

The amount of such a high-red-phosphorus-concentration product (E) mixed with the polyamide resin (A), the liquid-crystalline resin (B) and the thermoplastic polyester resin (C) depends on the amount of the red-phosphorus-high-concentration product. Polyamide resin (A) and liquid crystalline resin (B) from the viewpoints of properties, dispersibility of red phosphorus, and flame retardancy, mechanical properties, moldability and heat resistance of the finally obtained resin composition. And preferably 0.5 to 200 parts by weight, more preferably 1 to 180 parts by weight, more preferably 1 to 150 parts by weight, based on 100 parts by weight of the resin composition (D) composed of the thermoplastic polyester resin (C). It is.

The resin composition (E) having a high red phosphorus concentration
Is preferably used in the form of a so-called master pellet, but is not limited thereto, and may be in the form of a chip, a powder, or a mixture thereof. Also, a polyamide resin (A) blended with the component (E),
The liquid crystalline resin (B) and the thermoplastic polyester (C) are preferably in the form of pellets, but are not limited thereto, and may be in the form of a chip, a powder, or a mixture of a chip and a powder. It is preferable that the shapes, sizes, and shapes of the polyamide resin (A), the liquid crystal resin (B), and the thermoplastic polyester resin (C) are substantially the same or similar to each other because they can be uniformly mixed. In producing the resin composition, for example, a single-screw extruder equipped with a “Unimelt” type screw, a twin-screw extruder, a three-screw extruder, and a kneader of a kneader type are used.
The composition can be obtained by melt-kneading at 0 to 350 ° C.

The flame-retardant resin composition thus obtained is a composition excellent in fluidity, thin-walled flame retardancy, and heat resistance.
Even with a thickness of mm, it is possible to achieve the flame retardancy of UL-94 standard V-0.

Further, the molding method for molding the molded article is a usual molding method (injection molding, extrusion molding, blow molding, press molding, injection press molding, etc.) into 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.

Furthermore, the flame-retardant resin composition of the present invention can reduce defects such as unfilled, deformed and cracked due to lack of fluidity when obtaining molded articles requiring fluidity and thin flame retardancy. Yes, the obtained molded product has good flame retardancy and hydrolysis resistance, surface appearance and warpage of the molded product, and when used for housings and connectors, corrosion of nearby metal terminals etc. Due to the improvement, a highly reliable molded product can be obtained.

The molded article thus obtained is composed of various gears,
Various cases, sensors, LED lamps, connectors, sockets, paper separating claws, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, optical pickup slide base parts, oscillators, various terminal boards, transformers , Plugs, printed wiring boards,
Tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, housing, semiconductor, liquid crystal display parts, FD
D / carriage, FDD chassis, HDD parts, motor brush holders, parabolic antennas, electric / electronic parts such as computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, sound parts Audio equipment parts such as audio, laser disk, compact disk,
Homes represented by lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc.
Office electrical product parts, office computer related parts,
Telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, various bearings such as oilless bearings, stern bearings, underwater bearings, etc., motor parts, machine parts such as lighters and typewriters, microscopes , Binoculars, cameras, clocks, and other optical equipment, precision machinery-related parts, alternator terminals, alternator connectors, IC regulators, potentiometer bases for light drier, various valves such as exhaust gas valves, fuel-related, exhaust systems, intake systems Various 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 distributor, 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 plate, Step motor rotor, lamp socket, lamp reflector, lamp housing,
It is useful for automotive / vehicle-related parts such as brake pistons, solenoid bobbins, engine oil filters, ignition device cases, power seat gear housings, 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).

[0082]

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
(Manufactured by Toray Industries, Inc.). <A-2> Polyamide 6
Amilan CM1010 (manufactured by Toray Industries, Inc.) was used. <A-3> The following polyamide copolymer was produced as a polyamide 66 copolymer.

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 / cm2 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, and the relative viscosity was 2.63 (in sulfuric acid). , Melting point 27
8 ° C. polyamide 6T / 66 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)). <LCP2> 777 parts by weight of p-hydroxybenzoic acid,
126 parts by weight of 4,4'-dihydroxybiphenyl, 112 parts by weight of terephthalic acid, 519 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 816 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 62.
5 mol%, aromatic dioxy unit 7.5 mol%, ethylene dioxy unit 30 mol%, aromatic dicarboxylic acid unit 3
Melting point 225 ° C., 18 Pa · s (235
° C, orifice 0.5φ × 10mm, shear rate 1,000
(1 / sec)).

Each evaluation was measured according to the method described below. (1) Fluidity Injection speed 99%, injection pressure 300 using the following molding machine
kgf / cm 0.8mm thickness × 150mm × 1 in the ^second condition
The flowability (flow length) was measured using a 50 mm square test piece. (2) Swelling resistance Using a molding machine described below, the specimen was retained in a cylinder for 10 minutes at a cylinder temperature shown in Table 1, and a bending test piece was obtained. For 20 minutes, and the occurrence of blisters on the surface of the molded product was observed. The evaluation was ○: no defect, ×: defective. (3) Metal Corrosion Using the following molding machine, 1 /
An 8-inch Izod test piece was prepared, a 0.5 mm-thick copper plate was sandwiched between two Izod impact test samples, and the plate was treated in an oven at 150 ° C. for 100 hours, and the presence or absence of corrosion of the copper plate was observed.
Evaluation: ○: no corrosion, ×: corrosion. (4) Hydrolysis resistance AST at the cylinder temperature shown in Table 1 using the following molding machine
An M1 tensile test piece was prepared, treated for 1000 hours at 120 ° C. × 100% RH, subjected to a tensile test according to ASTM D638, and the degree of deterioration of the test piece due to hydrolysis was observed. Those with remaining toughness undergo ductile fracture, and those with severe deterioration undergo brittle fracture. The evaluation was 延: ductile fracture,
X: Brittle fracture. (5) Flame retardancy In accordance with UL-94, a 0.8 mm thick test piece was evaluated for flame retardancy. (6) Warp deformation 4-point gate length 40 mm x width 100 mm x height 10 mm
When a box-shaped molded product having a thickness of 1 mm was molded using the molding machine described below 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 8 20 parts by weight of red phosphorus (Nova Excel 140) was dry-blended with 100 parts by weight of LCP1, and the melting point of the liquid crystalline polyester was + 15 ° C. using a 30 mmφ twin screw extruder.
To obtain pellets of red phosphorus high concentration product (E1). A pellet of a red phosphorus-rich product (E2) produced in the same manner as in E1 except that LCP2 was used instead of LCP1 was obtained.

Next, in the proportions shown in Table 1, a polyamide resin, a liquid crystalline polyester, a thermoplastic polyester and a glass fiber (9 μm diameter, 3 mm length), a PAN-based carbon fiber (6 mm length) and a red phosphorus high concentration product (filler) were used as fillers. E1 or E2) or dry blend of red phosphorus, 30mmφ
And melt-kneaded at the cylinder temperature shown in Table 1 to obtain pellets. This pellet is used for Toshiba IS55EP
The specimen was supplied to an N injection molding machine (manufactured by Toshiba Machine Co., Ltd.), and a test piece was molded at the cylinder temperature shown in Table 1 and a mold temperature of 80 ° C. in accordance with the method for each evaluation item. Examples 8 and 9 The same evaluation as in Examples 1 and 6 was carried out by further adding succinic anhydride as an acid anhydride in the same composition as in Examples 1 and 6.

The addition method was as follows. A polyamide resin, an acid anhydride and a polyester resin were added at the temperature shown in Table 2 using a twin-screw extruder equipped with a side feeder, and a liquid crystalline polyester resin, a highly concentrated product and a filler were added to the side. It was added from a feeder to obtain a composition pellet. Next, the pellets were supplied to a Toshiba IS55EPN injection molding machine (manufactured by Toshiba Machine Co., Ltd.), and test pieces were molded at the cylinder temperature shown in Table 1 and the mold temperature of 80 ° C. by the method for each evaluation item.

As is clear from Table 1, the composition of the present invention is superior in flowability and thin-walled flame retardancy to the comparative example, free from surface appearance defects due to stagnation of the molded product, and obtained. The product has good hydrolysis resistance and metal corrosion resistance, and as shown in Table 2, the use of an acid anhydride improves the warp deformation of the molded product. It can be seen that the method is very excellent when obtaining molded articles such as.

[0088]

[Table 1]

[0089]

Industrial Applicability The thermoplastic resin composition of the present invention has improved fluidity, thin-walled flame retardancy and hydrolysis resistance, surface appearance, and metal corrosiveness. Electronics related equipment, precision machine related equipment, office equipment,
It is a material suitable for various other uses such as automobiles.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08L 69:00)

Claims (8)

[Claims] 1. A resin composition (D) comprising 100 parts by weight of a polyamide resin (A), 0.1 to 50 parts by weight of a liquid crystalline resin (B) and 0.1 to 50 parts by weight of a thermoplastic polyester resin (C). A flame-retardant resin composition comprising 0.01 to 30 parts by weight of red phosphorus per 100 parts by weight. 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. A reinforced flame-retardant resin composition comprising 100 parts by weight of the resin composition (D) and 0.5 to 300 parts by weight of a filler. 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, which has a flame retardancy of V-0 at a thickness of 0.8 mm according to UL-94 standard. 6. A resin composition having a red phosphorus concentration higher than the amount of red phosphorus to be actually blended into a thermoplastic resin composition by partially kneading a part of the resin component to be finally blended and red phosphorus. A method for producing a flame-retardant resin composition, comprising producing the flame-retardant resin composition according to any one of claims 1 to 5 after producing the resin composition. 7. A molded article comprising the flame-retardant resin composition according to any one of claims 1 to 5, wherein the molded article is a mechanical mechanism part, an electric / electronic part or an automobile part. . 8. A molded article comprising the flame-retardant resin composition according to any one of claims 1 to 5, 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.