JPH0959524A - Flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame retardant resin composition, having excellent flame retardance, heat resistance and fluidity and excellent in balance among mechanical characteristics such as weld strength and rigidity and useful as electrical and electronic parts, etc., by blending an organophosphorus-based compound with a tetrafluoroethylene polymer in a prescribed proportion. SOLUTION: This flame retardant resin composition is obtained by blending (C) 1-30 pts.wt. organophosphorus-based compound and (D) 0-5 pts.wt. trifluoroethylene polymer having 0.1-700μm average grain diameter and 2-2.3g/m<3> density based on 100 pts.wt. total amount of (A) 99-50wt.% thermoplastic resin and (B) 1-50wt.% thermotropic liquid crystal polyester. Furthermore, e.g. a phosphate-based oligomer of the formula [R1 to R4 are each a hydrocarbon residue; R5 to R8 are each H, a halogen or a hydrocarbon residue; X<1> to X<6> are each O or S; (q1 ) to (q6 ) are each 0 or 1; (n) is a number of 1-30 degree of polymerization] is preferred as the component (C).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame-retardant resin composition having an excellent balance of mechanical properties such as excellent flame retardancy, heat resistance, fluidity, weld strength and rigidity.

2. Description of the Related Art With the advanced use of plastics, plastics having various characteristics have been provided in recent years in response to market needs. Among them, thermotropic liquid crystal polymers that exhibit liquid crystallinity when melted are known to exhibit excellent fluidity and high elastic modulus due to self-strengthening due to a highly oriented rigid molecular chain. However, thermotropic liquid crystal polymers have various problems such as mechanical property anisotropy, molding shrinkage anisotropy, peeling due to fibrillation, and low weld strength due to a high degree of molecular chain orientation. On the other hand, a method of blending a liquid crystal polyester resin with an inorganic filler such as glass fiber has been proposed (for example, JP-A-63-264660 and JP-A-64-38464). There are problems that brittleness increases and weld strength and the appearance of molded products are not sufficient. Further, a method of melt-mixing polycarbonate, polyethylene terephthalate or the like with liquid crystal polyester (for example, JP-A-57-40551, JP-A-56-11537, JP-A-63-215769, JP-A-1-301749). Japanese Patent Laid-Open No. 2-26
No. 3849) was proposed, but injection molding is required because of high moldability, insufficient balance between heat resistance and moldability, and insufficient compatibility or dispersibility between components. It was not practically satisfactory, such as exfoliation of the product and less than the mechanical properties predicted from the mixing rule. On the other hand, aromatic polycarbonate is used in various fields such as OA equipment field and home appliances field due to its heat resistance and high toughness, but it has a drawback that heat resistance, fluidity, impact resistance, etc. are insufficient depending on the intended use. have.
By the way, it is generally known that the thermotropic liquid crystal polymer itself is flame-retardant because it has a rigid molecular chain and has many aromatic ring components constituting the molecular chain. However, there is a drawback that the flame retardancy is not exhibited as the amount of other components such as the thermoplastic resin increases. A method of adding a flame retardant such as an organic bromine compound to a melt-mixed thermotropic liquid crystal polyester and a thermoplastic resin (for example, JP-A-3-17).
No. 9051) was proposed, but the balance of mechanical properties such as flame retardancy, heat resistance, fluidity, weld strength and rigidity was not practically satisfactory.

The present invention has been made in view of the above-mentioned problems of the prior art, and has an excellent balance of mechanical properties such as flame retardancy, heat resistance, fluidity, weld strength and rigidity. An object is to provide a flame-retardant resin composition which is excellent and can be used in a wide range of applications.

[0002]

Means for Solving the Problems The inventors of the present invention have earnestly made efforts to solve the above problems, and as a result, have conceived a flame-retardant resin composition having the following constitution. (A) Thermoplastic resin 99 to 50% by weight, (B) Thermotropic liquid crystal polyester 1 to 50% by weight, the above (A)
+ (B) = 100 parts by weight, 1 to 30 parts by weight of (C) an organophosphorus compound, (D) an average particle diameter of 0.1 to 700 μm and a density of 2 to ^2.3 g / cm ³ are added. A flame-retardant resin composition comprising 0 to 5 parts by weight of the tetrafluoroethylene polymer. Hereinafter, the present invention will be described in detail.

The component (A) thermoplastic resin used in the present invention is an aromatic polycarbonate, (rubber) modified thermoplastic resin composition, polysulfone, polyether sulfone,
Polyphenylene sulfide, polyphenylene ether,
Polybutylene terephthalate, polyethylene terephthalate, polyamide 6, polyamide 6,6, polyamide 4,6 and the like can be mentioned, preferably aromatic polycarbonate, (rubber) modified thermoplastic resin composition, polyamide 6, polyamide 4,6. Yes, more preferably aromatic polycarbonate, (rubber) modified thermoplastic resin composition, polyamide 4,6, particularly preferably aromatic polycarbonate, (rubber) modified thermoplastic resin composition, most preferably aromatic. It is polycarbonate.
These can be used alone or in combination of two or more. By using two or more kinds in combination, the characteristics of each thermoplastic resin can be exhibited. As a preferable combination when two kinds are used in combination, aromatic polycarbonate / polyamide 4,6, aromatic polycarbonate / (rubber) modified thermoplastic resin composition, and polyamide 4,6 / (rubber) modified thermoplastic resin are particularly preferable. Is an aromatic polycarbonate / (rubber) modified thermoplastic resin composition. When two kinds are used in combination, the preferable component ratio is 10 by weight.
~ 90 / 90-10, more preferably 20-80 / 8
0 to 20.

Examples of the polycarbonate used in the present invention include those obtained by reacting various dihydroxyaryl compounds with phosgene, or those obtained by transesterification of dihydroxyaryl compounds with diphenyl carbonate. A typical example is 2,2'-bis (4-hydroxyphenyl).
It is a polycarbonate obtained by the reaction of propane and phosgene. Examples of the dihydroxyaryl compound used as a raw material for polycarbonate include bis (4-hydroxyphenyl) methane, 1,1′-bis (4-hydroxyphenyl) ethane, 2,2′-bis (4-hydroxyphenyl) propane, 2, 2'-bis (4-hydroxyphenyl) butane, 2,2'-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2'-bis (4-hydroxy-3-methyl) Phenyl) propane, 2,2'-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2'-bis (4-hydroxy-3-promophenyl) propane,
2,2'-bis (4-hydroxy-3,5-dichlorophenyl) propane, 1,1'-bis (4-hydroxyphenyl) cyclopentane, 1,1'-bis (4-hydroxyphenyl) cyclohexane, 4, 4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,
3'-dimethyldiphenyl ether, 4,4'-dihydroxyphenyl sulfide, 4,4'-dihydroxy-
3,3'-dimethylphenyl sulfide, 4.4'-dihydroxyphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethylphenyl sulfide, 4,4 '
-Dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethylphenyl sulfoxide, 4,4'-dihydroxyphenyl sulfone, 4,
There are 4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, hydroquinone, resorcin, and the like, and these are used alone or in combination of two or more. Particularly preferred is 2,2'-bis (4-hydroxyphenyl) propane (bisphenol A). The viscosity average molecular weight of the polycarbonate is preferably 15,000 to 40,0.
00, more preferably 17,000 to 35,000.

The (rubber) modified thermoplastic resin composition used in the present invention comprises an aromatic vinyl compound, a vinyl cyan compound, a (meth) acrylic acid ester and an acid anhydride in the presence of the rubbery polymer (a). Graft copolymer obtained by polymerizing at least one monomer selected from the group of monomers (b) consisting of a base monomer and a maleimide compound, or a group of monomers (b) It is at least one (rubber) -modified thermoplastic resin composition selected from polymers of at least one selected monomer. Examples of the rubber-like polymer (a) used in the (rubber) modified thermoplastic resin composition include polybutadiene, polyisoprene, butyl rubber, styrene-
Butadiene copolymer (styrene content is preferably 5 to 60% by weight), styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, ethylene-α-olefin copolymer, ethylene-α-olefin-polyene copolymer, Silicon rubber, acrylic rubber, butadiene- (meth) acrylic acid ester copolymer, polyisoprene, styrene-butadiene block copolymer, styrene-isoprene block copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated butadiene Examples thereof include a polymer and an ethylene ionomer. Styrene-
The butadiene block copolymer and the styrene-isoprene block copolymer include AB type, ABA type, taper type,
Those having a radial teleblock type structure are included. Further, the hydrogenated butadiene-based polymer is a hydride of the block copolymer of the styrene block and the styrene-butadiene random copolymer in addition to the hydride of the block copolymer, and the content of 1,2-vinyl bond in polybutadiene. Of 20% by weight or less and a hydride of a polymer comprising a polybutadiene block having a 1,2-vinyl bond content of more than 20% by weight. Examples of the aromatic vinyl constituting the component (b) include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene,
N, N-diethyl-P-aminoethylstyrene, N, N
-Diethyl-P-aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, ethylstyrene, vinylnaphthalene, etc. are particularly preferable, and styrene and α-methylstyrene are particularly preferable. . These aromatic vinyls may be used alone or in combination of 2
Used as a mixture of two or more species. As vinyl cyanide,
There are acrylonitrile, methacrylonitrile, etc. 1
They may be used alone or as a mixture of two or more. Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amino acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate and benzyl acrylate. Acrylic acid ester of; methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, amino methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate,
There are methacrylic acid esters such as cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate and benzyl methacrylate, and these are used alone or in combination of two or more. Examples of the acid anhydride-based monomer include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. Examples of the maleimide compound include maleimide compounds of α, β-unsaturated dicarboxylic acids such as maleimide, N-methylmaleimide, N-butylmaleimide, N- (P-methylphenyl) maleimide, N-phenylmaleimide and N-cyclohexylmaleimide. The compounds are used alone or in combination of two or more. The aromatic vinyl, vinyl cyanide, (meth) acrylic acid ester, acid anhydride monomer and maleimide compound are used alone or in combination of two or more. In addition, 30 other vinyl monomers copolymerizable with the above monomers are added.
It is also possible to perform copolymerization in an amount of not more than wt%. As these monomers, glycidyl methacrylate, unsaturated epoxy compounds such as allyl glycidyl ether, acrylamide,
Unsaturated carboxylic acid amides such as methacrylamide; amino group-containing unsaturated compounds such as acrylic amine, aminomethyl methacrylate, aminoethyl methacrylate, aminopropyl methacrylate, aminostyrene; hydroxystyrene, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene,
Unsaturated hydroxyl group-containing compounds such as trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate; acrylic acid, methacrylic acid, itaconic acid, There are unsaturated acids such as maleic acid, and unsaturated compounds containing an oxazoline group such as vinyl oxazoli, and these are used alone or in combination of two or more.

The (rubber) -modified thermoplastic resin composition may be one obtained by graft-polymerizing a vinyl monomer in the presence of the rubber-like polymer, or in the absence of the rubber-like polymer and vinyl monomer. What polymerized the monomer, or these may be mixed. The preferable amount of the rubber-like polymer in the (rubber) modified thermoplastic resin composition is 5 to 5 from the viewpoint of impact resistance.
It is 80% by weight, more preferably 10 to 70% by weight. Further, the average dispersion diameter of the rubber-like polymer in the rubber-modified thermoplastic resin composition is preferably 0.0 in terms of impact resistance.
1 to 50 μm, more preferably 0.05 to 30
μm. The (rubber) modified thermoplastic resin can be produced by known polymerization methods such as emulsion polymerization, solution polymerization, suspension polymerization and bulk polymerization. The graft ratio in the graft copolymer is preferably 5 to 200% by weight, more preferably 10 to 150% by weight. Also, the intrinsic viscosity (η) of the methyl ethyl ketone soluble component (in methyl ethyl ketone, 3
The measurement at 0 ° C.) is preferably 0.1 to 1.2 dl / g, and more preferably 0.2 to 0.8 dl / g. (A)
When two or more kinds of the monomer (b) components are polymerized in the presence of the components, preferable combinations are listed below. 1) Aromatic vinyl compound / vinyl cyanide compound 2) Aromatic vinyl compound / (meth) acrylic acid ester 3) Aromatic vinyl compound / vinyl cyanide compound / (meth) acrylic acid ester 4) Aromatic vinyl compound / maleimide Monomer 5) Aromatic vinyl compound / vinyl cyanide compound / maleimide monomer 6) Aromatic vinyl compound / (meth) acrylic acid ester / maleimide monomer 7) Aromatic vinyl compound / vinyl cyanide Compound / acid anhydride monomer 8) Aromatic vinyl compound / (meth) acrylic acid ester / acid anhydride monomer 9) Aromatic vinyl compound / vinyl cyanide compound / (meth) acrylic acid ester / acid Anhydride monomer 10) Aromatic vinyl compound / maleimide monomer / acid anhydride monomer 11) (meth) acrylic acid ester monomer Polymers that may be optionally added to the shift copolymer,
It is obtained by polymerizing at least one selected from the group of monomers (b). Preferred polymers are listed below. 1) Aromatic vinyl compound-vinyl cyanide compound copolymer 2) (Meth) acrylic acid ester polymer 3) Aromatic vinyl compound polymer 4) Aromatic vinyl compound-maleimide monomer copolymer 5) Aroma Group vinyl compound-maleimide monomer-vinyl cyanide compound copolymer 6) Aromatic vinyl compound-maleimide monomer-acid anhydride monomer copolymer 7) Aromatic vinyl compound- (meth) acryl Acid ester- (vinyl cyanide compound) copolymer

Polyamides 4 and 6 are polytetramethylene adipamides obtained from tetramethylene diamine and adipic acid, and include a copolyamide having polytetramethylene adipamide units as a main constituent. The copolymerization component is not particularly limited, and a known amide-forming component can be used. As a typical example of the copolymerization component, 6-
Aminocaproic acid, 11-aminoundecanoic acid, 12-
Amino acids such as aminoundecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-lauryllactam, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4
-/ 2,4,4-trimethylhexamethylenediamine,
5-methylnonamethylenediamine, metaxylenediamine, paraxylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) siloxyhexane, 1-amino-3-aminomethyl-3,
Diamines such as 5,5-trimethylcyclohexane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, 2,2-bis (aminoprosyl) piperazine, and aminoethylpiperazine Adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid, hexahydroterephthalate Examples thereof include acids and dicarboxylic acids such as hexahydroisophthalic acid and diglycolic acid. The method for producing the polyamides 4 and 6 used in the present invention is arbitrary. For example, JP-A-56-149430 and JP-A-56-14943.
No. 1, JP-A-58-83029, JP-A-61-43631, etc., that is, first, a prepolymer having a small number of cyclic end groups is produced under specific conditions, and then this is prepared. A method for preparing high-viscosity polyamides 4 and 6 by solid phase polymerization in a steam atmosphere, or 2-
There is a method of obtaining it by heating in a polar organic solvent such as pyrrolidone or N-methylpyrrolidone. The degree of polymerization of polyamides 4 and 6 is not particularly limited,
In 96% sulfuric acid, the relative viscosity at 1 g / dl is 2.0 to
Polyamides 4,6 in the range of 6.0 are preferably used. However, the relative viscosity is a value obtained by V / V ₀ , where V is the viscosity of a solution in which a resin is dissolved and V ₀ is the viscosity of a solvent. In the present invention, 96% sulfuric acid is used as the solvent. And the solution concentration is 1 g / d
l (dl: deciliter, 1 dl = 100 ml),
It measured at 25 degreeC using the viscosity tube.

The amount of the component (A) used in the present invention is 99.
-50% by weight, preferably 95-55% by weight, more preferably 90-60% by weight, particularly preferably 90-70%.
% By weight. When the amount of the component (A) used exceeds 99% by weight, flame retardancy, heat resistance, fluidity, and rigidity decrease, and
If it is less than 0% by weight, the balance of weld strength and mechanical properties such as toughness, boss strength, and hinge characteristics is deteriorated, which is not preferable. As the polyester used in the present invention, known ones can be used as the thermotropic liquid crystal polyester which is the component (B) of the present invention. For example, a thermotropic liquid crystal polyester mainly composed of p-hydroxybenzoic acid and polyethylene terephthalate, p
Liquid crystalline polyester having hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid as main constituent units, and thermotropic liquid crystal polyester having p-hydroxybenzoic acid and 4,4'-dihydroxybiphenyl and terephthalic acid as main constituent units There is no particular limitation. Further, in the component (B) of the present invention, those comprising the following structural units (a), (b) and, if necessary, (c) and / or (d) can be preferably used.

[0009]

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Here, the structural units (a) and (b) are the structural unit of the polyester produced from p-hydroxybenzoic acid and the structural unit produced from 2-hydroxy-6-naphthoic acid, respectively. ) And (b), it is possible to obtain the thermoplastic resin composition of the present invention having an excellent balance of mechanical properties such as excellent flame retardancy, heat resistance, fluidity, weld strength and rigidity. . X in the structural units (c) and (d) can be arbitrarily selected from the chemical formula 5 and / or the chemical formula 6 and one or more types can be selected. By selecting X in the structural unit from among X _{1 in} Chemical Formula 5, a resin composition having relatively good heat resistance and rigidity can be obtained. Further, by selecting X from among X _{2 in} Chemical Formula 6, a resin composition having a relatively good balance of moldability and mechanical properties can be obtained.

[0011]

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[Chemical 6]

In the structural formula (C), preferred are structural units formed from ethylene glycol, hydroquinone, p-hydroxybiphenyl, 2,6-dihydroxynaphthalene and bisphenol A, and more preferred are ethylene glycol and hydroquinone. , P
-Hydroxybiphenyl, particularly preferred are ethylene glycol and hydroquinone. Structural formula (d) is preferably a structural unit formed from terephthalic acid, isophthalic acid or 2,6-dicarboxynaphthalene, more preferably terephthalic acid or isophthalic acid, and particularly preferably It is terephthalic acid. As for the structural formula (C) and the structural formula (D), at least one kind or two or more kinds of the structural units listed above can be used in combination. Specifically, in the case of using two or more kinds in combination, in the structural formula (c), 1) a structural unit generated from ethylene glycol / a structural unit generated from hydroquinone, 2) a structural unit generated from ethylene glycol / p-hydroxy Structural units generated from biphenyl, 3) structural units generated from hydroquinone / structural units generated from p-hydroxybiphenyl, and the like can be mentioned. Further, in the structural formula (d), 1)
Examples thereof include a structural unit formed from terephthalic acid / a structural unit formed from isophthalic acid, 2) a structural unit formed from terephthalic acid / 2, a structural unit formed from 2,6-dicarboxynaphthalene, and the like. Here, the amount of terephthalic acid in the two components is preferably 40% by weight or more, more preferably 60% by weight or more, and particularly preferably 80% by weight or more. When the amount of terephthalic acid is 40% by weight or more in the two components, the resin composition has relatively good fluidity and heat resistance. The proportions of the structural units (a), (b), (c) and (d) used are not particularly limited. However, structural unit (c)
And (d) are basically almost equimolar amounts. In addition, the structural unit (e) chemical formula 7 consisting of the structural units (c) and (d)
It can also be used as a structural unit in the component (A).

[0013]

[Chemical 7]

Specifically, 1) a structural unit formed from ethylene glycol and terephthalic acid, 2) a structural unit formed from hydroquinone and terephthalic acid, 3) a structural unit formed from p-hydroxybiphenyl and terephthalic acid,
4) Structural units formed from 2,6-dihydroxynaphthalene and terephthalic acid, 5) Structural units formed from bisphenol A and terephthalic acid, and the like. In the component (B) of the present invention, a structural unit formed from other aromatic dicarboxylic acid, aromatic diol, or aromatic hydroxycarboxylic acid is optionally contained in a small amount so as not to impair the object of the present invention. Can be introduced. The component (B) of the present invention preferably has a temperature at which it starts to show a liquid crystal state at the time of melting (hereinafter referred to as liquid crystal starting temperature) of 150 to
The temperature is 350 ° C, more preferably 180 to 320 ° C, and particularly preferably 200 to 300 ° C. Setting the liquid crystal starting temperature within this range makes the resulting resin composition well balanced in preferable rigidity, moldability and mechanical properties. Further, by setting the liquid crystal starting temperature to 150 to 250 ° C., it is particularly preferable in terms of surface appearance of the molded product. Further, by setting the liquid crystal starting temperature to 250 to 350 ° C., it is possible to maintain the wear resistance, chemical resistance, rigidity, creep resistance, rib strength and the like of the obtained composition at a high temperature within a preferable range. The heat distortion temperature of the component (B) of the present invention (ASTM D6
According to 48, 1/8 "thickness x 1/2" width x 5 "length, load 1
8.6 kg / cm ² ) is preferably 130 to 300
C., more preferably 150 to 280.degree. C., particularly preferably 170 to 250.degree. By setting the heat distortion temperature within this range, the resin composition obtained has a relatively good balance between favorable heat resistance and mechanical properties. Further, by setting the heat distortion temperature to 130 to 210 ° C., a resin composition having relatively good fluidity, moldability, boss cracking, hinge characteristics and the like can be obtained. Further, by setting the heat distortion temperature to 210 to 300 ° C., the creep resistance and rigidity of the obtained resin composition at high temperatures can be made relatively good, and the molding cycle in injection molding can be made relatively short. The loss tangent (tan δ) of the component (B) of the present invention at 25 ° C. is preferably 0.03 to.
It is 1.5, more preferably 0.05 to 1.5, and particularly preferably 0.07 to 1.5. Setting the loss tangent within this range makes the vibration damping performance of the resulting composition preferable. Apparent melt viscosity of component (B) of the present invention (liquid crystal starting temperature + 30 ° C., shear rate 100 / sec)
Is preferably 100 to 30,000 poise, more preferably 100 to 20,000 poise, and particularly preferably 10
It is 0 to 10000 poise. Setting the apparent melt viscosity within this range makes the flowability of the resulting composition preferable. The thermal conductivity of the component (B) of the present invention in the molten state (liquid crystal state) is preferably 0.1 to 2.0 W.
/ MK, more preferably 0.2 to 1.5 W / mK, and particularly preferably 0.3 to 1.0 W / mK. By setting the heat conductivity in the molten state (liquid crystal state) within this range, the injection molding cycle of the obtained composition can be relatively shortened. The amount of the component (B) used in the present invention is 1 to
It is 50% by weight, preferably 5 to 45% by weight, more preferably 10 to 40% by weight, and particularly preferably 10 to 30% by weight. When the amount of the component (B) used exceeds 50% by weight, the balance of weld strength and mechanical properties such as toughness, boss strength, and hinge properties decreases, and when it is less than 1% by weight, flame retardancy, heat resistance, fluidity and It is not preferable because the rigidity decreases.

The component (C) used in the present invention is an organic phosphorus compound. Examples of the organic phosphorus compound include phosphates typified by triphenyl phosphate and phosphates typified by trophenyl phosphite. For example, the organophosphorus compound has at least one structural unit represented by the following general formulas 8 to 11. It is a compound.

[0016]

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(In the formula, R _{1 to} R ₃ are each a hydrocarbon residue which may be halogen-substituted, X ^{1 to} X ⁴ are oxygen atoms or sulfur atoms, and q _{1 to} q ₃ are 0 or 1. )

[0018]

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(Wherein R₁~ R_FourIs a halogen storage
Optionally substituted hydrocarbon residue, R _Five~ R₈Is hydrogen
Child, halogen atom or hydrocarbon residue, X¹~ X⁶Is acid
Elementary atom or sulfur atom, q₁~ Q₆Is 0 or 1, n
Indicates a number having a degree of polymerization of 1 to 30. )

[0020]

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(In the formula, R _{1 to} R ₅ are each a hydrocarbon residue which may be substituted with halogen, R _{6 to} R ₁₃ are hydrogen atoms, halogen atoms or hydrocarbon residues, and X ^{1 to} X ⁸ are oxygen. Atom or sulfur atom, q _{1 to} q ⁷ are 0 or 1, n
Indicates a number having a degree of polymerization of 1 to 30. )

[0022]

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(In the formula, R _{1 to} R ₆ are each a hydrocarbon residue which may be halogen-substituted, R _{7 to} R ₉ are hydrogen atoms, halogen atoms or hydrocarbon residues, and X ^{1 to} X ¹² are oxygen. Atom or sulfur atom, q _{1 to} q ₉ represent 0 or 1.) These organic phosphorus compounds may be used alone or in combination of two or more kinds. In the present invention, triphenyl phosphate, tri-2,6-dimethylphenyl phosphate, tricresyl phosphate, diphenyl-2-, which are represented by the chemical formula 8, are used as the organic phosphorus compound.
Ethyl cresyl phosphate, tri- (isopropylphenyl) phosphate, and the phosphate-based oligomers represented by Chemical Formulas 9 to 10 are preferable, more preferably the phosphate-based oligomers represented by Chemical Formula 9 or Chemical Formula 10, and particularly preferably the chemical formula 9. It is the represented phosphate oligomer. The phosphate-based oligomer may have the chemical formula 9 and / or the chemical formula 10 as a main component, and may contain triphenyl phosphate or another organic phosphorus compound in an amount of less than 50% by weight. Preferred phosphate-based oligomers of Chemical Formula 9 include those containing a compound represented by the following Chemical Formulas 12 and 13 as a main component, and preferred phosphate-based oligomers of the Chemical Formula 10 are those of the following Chemical Formula 1
4 to those containing a compound represented by the chemical formula 16 as a main component.

[0024]

[Chemical 12]

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The amount of component (C) used in the present invention is
1 for 100 parts by weight of the total of the components (A) and (B)
-30 parts by weight, preferably 3 to 28 parts by weight, more preferably 5 to 25 parts by weight, particularly preferably 6 to 23 parts by weight. If the amount of component (C) used is less than 1 part by weight, the flame retardant effect is not observed, while if it exceeds 30 parts by weight, heat resistance, rigidity, weld strength and impact resistance are poor. In addition to the above organophosphorus compounds, known halogen-based flame retardants (A) +
With respect to (B) = 100 parts by weight, it can be used in an amount of preferably 20 parts by weight or less, more preferably 15 parts by weight or less. The combined use is preferable because the flame retardancy and mechanical properties of the flame retardant resin composition of the present invention are improved. When the amount of the halogen-based flame retardant used exceeds 20 parts by weight, heat resistance and impact resistance are poor, which is not preferable. Of the halogen-based flame retardants, preferably halogenated epoxy compounds, halogenated polycarbonate oligomers, halogenated phenyl ether compounds or polymers, halogenated styrene compound polymers or polystyrene halides, more preferably halogenated polycarbonate oligomers. Halogenated phenyl ether compound or polymer, halogenated styrene compound polymer or polystyrene halide, particularly preferably halogenated phenyl ether compound or polymer and halogenated styrene compound polymer or polystyrene halide. . Among the halogenated phenyl ether compounds or polymers, poly (dibromophenylene ether) and bis (tribromophenoxy) ethane are particularly preferable. In addition, the polymer of halogenated styrene compound or the halide of polystyrene is preferably poly (dibromostyrene) or poly (tribromostyrene), and a polymer obtained by polymerizing a halogenated styrene monomer or a polymer of styrene monomer is used. It may be halogenated later. An antimony-containing compound may be used to improve the flame retardant effect of the flame retardant. The preferred amount used to obtain the flame retardancy improving effect is (A) +
The amount is 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the total of the component (B). Further, examples of the antimony content include antimony trioxide, antimony tetraoxide, (colloidal) antimony pentoxide, sodium antimonate and antimony phosphate, among which antimony trioxide is preferable.

The tetrafluoroethylene polymer of the component (D) of the present invention has an average particle size of 0.1 to 700 μm, preferably 0.5 to 500 μm, and more preferably 5 to 4 μm.
00 μm, particularly preferably 25 to 300 μm. 70
If it exceeds 0 μm, impact resistance and weld strength are poor. The density of ^{2g / cm 3 ~2.3g / cm 3} , preferably of powder form 2.1~2.2g / cm ^3. The average molecular weight is preferably 500,000 or more, more preferably 1,000,000 to 5,000,000.
The component (D) is preferably obtained by suspension polymerization in order to achieve the object of the present invention. The amount of the component (D) used in the present invention is 0 to 5 parts by weight, preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight based on 100 parts by weight of the total of the components (A) + (B). Parts by weight, particularly preferably 0.1
1 part by weight. If the amount used exceeds 5 parts by weight, the weld strength and impact resistance are poor, which is not preferable. Further, by using the component (D) in the resin composition of the present invention, dripping at the time of combustion can be remarkably suppressed, and thus it is preferably used. For the purpose of improving the mechanical properties of the flame-retardant resin composition of the present invention, glass fiber, carbon fiber, metal fiber, metal flake, glass beads, wollastonite, rock filler, calcium carbonate, talc, mica, glass flake The fillers such as milled fiber, kaolin, barium sulfate, graphite, molybdenum disulfide, magnesium oxide, zinc oxide whiskers and potassium titanate whiskers can be used alone or in combination. Among these fillers, glass fibers and carbon fibers preferably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more. These fillers are usually used in the range of 5 to 150 parts by weight with respect to 100 parts by weight of the composition of the present invention. Further, the composition of the present invention may be mixed with known additives such as coupling agents, light stabilizers, antioxidants, plasticizers, colorants, lubricants, antistatic agents, silicone oils, foaming agents and the like. . In addition, the composition of the present invention,
By incorporating an antibacterial agent such as silver or a silver compound or a commercially available antifungal agent, excellent antibacterial and antifungal properties can be imparted. The content of such antibacterial agent and antifungal agent is 0.01 to 30% by weight, preferably 0.05 to 20% by weight. Further, the flame-retardant resin composition of the present invention can be appropriately blended with a compound or polymer having at least one epoxy group or acid anhydride group, if necessary. Among them, a multi-phase structure polymer is preferable. A multi-phase structure polymer is a main chain copolymer obtained by copolymerizing a compound mainly composed of an unsaturated compound having an olefin and at least one functional group selected from an epoxy group and an acid anhydride group, with an aromatic compound. It is a graft copolymer having a multiphase structure obtained by graft-polymerizing at least one monomer selected from group vinyl compounds, vinyl cyan compounds, and (meth) acrylic acid esters. Specific examples of the olefin in the multiphase structure include ethylene and propylene, butene-1, 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, and other α-olefins, and ethylene. , Propylene is preferable, and ethylene is particularly preferable. Also,
The unsaturated compound having an epoxy group, glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, butyl carboxylic acid esters,
Allyl glycidyl ether, 2-methyl allyl glycidyl ether, styrene-p-glycidyl ether, 3,
4-epoxybutene, 3,4-epoxy-3-methyl-
1-butene, 3,4-epoxy-1-pentene, 3,4
-Epoxy-3-methylpentene, 5,6-epoxy-
1-hexene, vinylcyclohexene monoxide, p
-Glycidyl styrene and the like can be mentioned, and glycidyl methacrylate is preferable.

Examples of the unsaturated compound having an acid anhydride group in the multi-phase structure polymer include maleic anhydride, itaconic anhydride, citraconic anhydride and the like, and maleic anhydride is preferred. The unsaturated compound having at least one functional group selected from an epoxy group and an acid anhydride group can be used alone or in combination of two or more. Further, in the main chain copolymer formed by copolymerizing these with olefin,
Other unsaturated compounds such as ethyl acrylate can be used if desired. The amount of the other unsaturated compound in the main chain copolymer is preferably 30% by weight or less in order to serve the original purpose of using the multiphase structure polymer. The content of the unsaturated compound having at least one functional group selected from the epoxy group and the acid anhydride group in the multi-phase structure polymer is 0.
It is 1 to 30% by weight, preferably 0.5 to 25% by weight, and more preferably 1 to 20% by weight. If it is less than 0.1% by weight in the multi-phase structure polymer, the effect due to the addition of the multi-phase structure polymer is not sufficiently exhibited, which is not preferable, and if it exceeds 30% by weight, molding heat stability and molding processability are deteriorated. It is not preferable. The content of the main chain copolymer in the multi-phase structure polymer is preferably 10 to 90% by weight, more preferably 40% by weight.
~ 80% by weight. As the aromatic vinyl compound, vinyl cyanide compound, and (meth) acrylic acid ester in the multi-phase structure polymer, those described above can be applied as they are. Among these, one kind may be used alone, or two or more kinds may be used in combination. If necessary, other compounds may be used in the range of 30% by weight or less. The multi-phase structure polymer is produced by a known method such as emulsion polymerization, solution polymerization, suspension polymerization. At this time, as the polymerization initiator, molecular weight modifier, emulsifier, dispersant, solvent, etc. used in the polymerization, those usually used in these polymerization methods can be used. The amount of the multi-phase structure polymer used is (A) + (B)
= 0.5 to 40 parts by weight, preferably 0.7 to 30 parts by weight, more preferably 1 to 20 parts by weight, and particularly preferably 1 to 15 parts by weight with respect to 100 parts by weight. By using the multi-phase structure polymer in this range, the resulting flame-retardant resin composition has a much better balance of mechanical properties such as weld strength and rigidity. If it exceeds 40 parts by weight, heat resistance, fluidity, weld strength, rigidity and the like are deteriorated, which is not preferable.

The flame-retardant resin composition of the present invention can be obtained by kneading the components using various extruders, Banbury mixers, kneaders, rolls and the like. A preferred manufacturing method is a method using a twin-screw extruder. Moreover, when kneading each component, you may knead all components collectively, and you may knead them by a multistage addition system. The flame-retardant resin composition of the present invention thus obtained is molded into various molded articles by injection molding, sheet extrusion, vacuum molding, profile extrusion molding, blow molding, foam molding, injection press molding, gas injection molding, etc. can do. The various molded products obtained by the above-mentioned molding method utilize OA.
It can be used for various parts, housings, chassis, etc. in the fields of home appliances, electric and electronic fields, sundries, sanitary fields, automobile fields, etc.

[0029]

EXAMPLES The present invention will be further described below with reference to examples.
You. In the examples, parts and% are weights unless otherwise specified.
It is a quantity standard. The various evaluations in the examples are as follows.
Is the value measured.Heat-resistant Measure the heat distortion temperature (° C) according to ASTM D648
Was.Liquidity Slab flow with a cylinder temperature of 290 ° C and a thickness of 0.5 mm
-Using a mold, injection pressure 1000kg / cm²Flow length
Was evaluated and evaluated as follows. ◎: Very good flow ○: Good flow ×: Not good flowWeld strength Weld line is formed in the center of ASTM No. 1 dumbbell
The tensile strength (T
M), and then make a mold with no weld line.
Tensile strength (To) was measured using shaped test pieces.
Weld strength is calculated by the following formula from the tensile test (TM, To).
According to the above, the retention rate of the weld strength was obtained. Retention rate (%) = (TM / To) × 100rigidity Bending modulus is measured according to ASTM D790
Was. Unit is kg / cm² Flame retardance Observe the combustion state after contacting the test piece with flame and judge with ○ ×
Was. X: Continued to burn. ○: It disappeared naturally.Thermoplastic resin (A) -1 to (A) -11 As the component (A) of the present invention, the following (A) -1 to (A)-
11 was used. 1. Aromatic polycarbonate: (A) -1, (A) -2 Viscosity average molecule obtained by polymerization of bisphenol A and phosgene
The following two types having different amounts were used. (A) -1: molecular weight 21,000 (A) -2: molecular weight 25,000 2. (Rubber) modified thermoplastic resin composition: (A) -3 to
(A) -6 As (a) component used in (rubber) modified thermoplastic resin
The rubbery polymer shown in Table 1 was used. Rubbery polymer (a)-
Various monomers were graft-polymerized in the presence of 1 to (a) -3.
No resin and rubbery polymer, only monomer component
Polymerized resins were obtained. The composition of these resins
The results are shown in Table 2. (A) -3 and (A) -4 are emulsion polymerization,
(A) -5 and (A) -6 were obtained by solution polymerization.

[0030]

[Table 1]

[Table 2]

3. Polyamide 4,6: (A) -7 ~
(A) -9 (A) -7: DSM, Netherlands, relative viscosity 2.2 (A) -8: DSM, Netherlands, relative viscosity 3.0 (A) -9: DSM, Netherlands , Relative viscosity 4.5 thermotropic liquid crystal polyester (B) -1 to (B)
- 9 In a nitrogen atmosphere, p- hydroxybenzoic acid, 2-
A thermotropic liquid crystal polyester having the following theoretical structural formula was obtained by heating and melting using hydroxy-6-naphthoic acid, a diol, and a dicarboxylic acid component and polycondensing. The component composition ratio represents a molar ratio.

(B) -1

Embedded image (B) -2

Embedded image (B) -3

Embedded image (B) -4

Embedded image (B) -5

[Chemical 21] (B) -6

Embedded image (B) -7

Embedded image

(C) -1 to (C) -6 (B) -8

Embedded image (B) -9

Embedded image The following compounds were used as the organic phosphorus compounds (C) -1 to (C) -6 organic phosphorus compounds. (C) -1: A phosphate-based oligomer having Chemical Formula 7 as a main component. (C) -2: A phosphate-based oligomer having Chemical Formula 8 as a main component. (C) -3: a phosphate-based oligomer having Chemical Formula 9 as a main component. (C) -4: a phosphate-based oligomer having Chemical Formula 10 as a main component. (C) -5: A phosphate-based oligomer having Chemical Formula 11 as a main component. (C) -6: Triphenyl phosphate In addition, the amount of the main components in (C) -1 to (C) -5 was 50% by weight or more. Tetrafluoroethylene polymer (D) As the component (D) of the present invention, powdery tetrafluoroethylene polymer (D) -1 was used. (D) -1: ^R Hostaflon TF1620 (average particle diameter 220 μm, density 2.15 g / cm ² ) manufactured by Hoechst Co., Ltd. Further, as a comparative example, a toterafluoroethylene polymer having an average particle diameter outside the range of the present invention (D). -2 was used.
(D) -2: ^R Hostaflon TF1502 (average particle size 800 μm, density 2.16 g / cm ² ) manufactured by Hoechst Co., Ltd. Filler (E) -1, (E) -2 The following (E) -1, as a filler, (E) -2 was used. (E) -1: Carbon fiber; Asahi Fiber Glass Co., Ltd.
A9000 (E) -2: glass fiber; EC manufactured by Nippon Electric Glass Co., Ltd.
S-03-F34

Examples 1 to 21 and Comparative Examples 1 to 6 Using the compounding recipes shown in Tables 3 and 4, melt-kneading was carried out using a vented twin-screw extruder and pelletized. Using this pellet, a test piece was prepared by an injection molding machine and evaluated by the above evaluation method. The evaluation results are also shown in Tables 3 and 4. Examples 1 to 21 are flame-retardant resin compositions of the present invention, which are excellent in flame retardancy, heat resistance, fluidity, welded strength, and rigidity, and their balance is particularly excellent. In contrast,
In Comparative Example 1, the components (A) and (B) are out of the range of the present invention, and the flame retardancy, heat resistance, fluidity and rigidity are poor. In Comparative Example 2, the components (A) and (B) are out of the range of the present invention, and the weld strength is poor. In Comparative Example 3, the component (C) is out of the range of the present invention and the flame retardancy is poor. Comparative Example 4
The component (C) is out of the range of the present invention, and the heat resistance and rigidity are poor. In Comparative Example 5, the component (D) is outside the scope of the present invention,
Poor weld strength. In Comparative Example 6, the component (D) is out of the range of the present invention, and the weld strength is poor.

[0035]

[Table 3]

[Table 4]

[0036]

The flame-retardant resin composition of the present invention has an excellent balance of mechanical properties such as excellent flame retardancy, heat resistance, fluidity, weld strength and rigidity. Therefore, electric / electronic parts, acoustic members, and OA that require these performances
It can be used for various structural materials, housings and parts in the fields of equipment, home appliances and vehicles.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI technical display location C08L 67:00) (72) Inventor Hisao Nagai 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Naru Rubber Co., Ltd.

Claims (1)

[Claims] 1. A thermoplastic resin of 99 to 50% by weight,
(B) 1 to 50% by weight of thermotropic liquid crystal polyester, (A) + (B) = 100 parts by weight,
1 to 30 parts by weight of (C) an organophosphorus compound, (D) 0.
1-700 μm average particle size and 2-2.3 g / cm ³
A flame-retardant resin composition containing 0 to 5 parts by weight of a tetrafluoroethylene polymer having a density of.