JPH0931339A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin compsn. which is excellent in flame retardance, heat resistance, flowability, and weld strength and in the balance among mechanical characteristics such as stiffness by compounding a thermo plastic resin with a specific thermotropic liq.-crystalline polyester and a halogen flame retardant. SOLUTION: This resin compsn. is prepd. by compounding 100 pts.wt. polymer component comprising 99-50wt.% thermoplastic resin and 1-50wt.% thermotropic liq.-crystalline polyester represented by formula I, formula II, and according to need formula III and/or formula IV with 1-50 pts.wt. halogen flame retardant and can be molded into various articles by injection molding, sheet extrusion- vacuum forming, profile extrusion, blow molding, foam molding, injection press molding, gas injection molding, etc. Articles produced from the compsn. by those molding methods, having excellent properties, can be applied for parts, housings, chassis, etc., in the fields of office automation, electric home appliances, electric and electronic appliances, miscellaneous goods, sanitary goods, automobilies, etc.

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) the following structural unit (A),
(B), and optionally (c) and / or (d) thermotropic liquid crystal polyester 1 to
50% by weight,

[0003]

[Chemical 1]

[0004]

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[0005]

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[0006]

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A flame-retardant resin composition comprising 1 to 50 parts by weight of (C) a halogen-based flame retardant, based on 100 parts by weight of (A) + (B). 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 the reaction of various dihydroxyaryl compounds with phosgene, or those obtained by the transesterification reaction of a dihydroxyaryl compound 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 above-mentioned aromatic vinyl, vinyl cyanide,
The (meth) acrylic acid ester, the acid anhydride monomer and the maleimide compound are used alone or in combination of two or more. Further, 30% by weight or less of another vinyl monomer copolymerizable with the above monomer may be copolymerized. As these monomers, unsaturated epoxy compounds such as glycidyl methacrylate and allyl glycidyl ether, unsaturated carboxylic acid amides such as acrylamide and methacrylamide; acrylamine, aminomethyl methacrylate, aminoethyl methacrylate, aminopropyl methacrylate,
Amino group-containing unsaturated compounds such as aminostyrene; hydroxystyrene, 3-hydroxy-1-propene, 4-
Hydroxy-1-butene, cis-4-hydroxy-2-
Butene, trans-4-hydroxy-2-butene, 3-
Hydroxyl-2-methyl-1-propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and other unsaturated compounds containing hydroxyl groups; unsaturated acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and vinyl sixazol. And oxazoline group-containing unsaturated compounds, and these are used alone or in combination of two or more.

The (rubber) modified thermoplastic resin composition may be 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 copolymerized polyamides 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, heat resistance, fluidity and rigidity decrease, and
If it is less than the above range, the balance of weld strength and mechanical properties such as toughness, boss strength, and hinge properties deteriorates, which is not preferable. The thermotropic liquid crystal polyester of the component (B) used in the present invention comprises the above structural units (a), (b) and, if necessary, (c) and / or (d). Here, the structural units (a) and (b) are respectively p-
A structural unit of polyester produced from hydroxybenzoic acid and a structural unit produced from 2-hydroxy-6-naphthoic acid, which are essential components in the component (B). By using the structural units (a) and (b) as an essential component, the thermoplastic resin composition of the present invention having an excellent balance of mechanical properties such as excellent heat resistance, fluidity, weld strength and rigidity is obtained. be able to. The structural unit (C),
X in (d) can be arbitrarily selected from the chemical formula 5 and / or the chemical formula 6, respectively, or 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.

[0015]

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[0016]

[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 amounts of the structural units (a), (b), (c) and (d) in the component (B) used in the present invention are not particularly limited. However, the structural units (C) and (D) are basically almost equimolar amounts. Further, the chemical unit (7), which is a structural unit consisting of the structural units (C) and (D), can be used as the structural unit in the component (B). Specifically, 1) a structural unit formed from ethylene glycol and terephthalic acid,
2) Structural unit produced from hydroquinone and terephthalic acid, 3) Structural unit produced from p-hydroxybiphenyl and terephthalic acid, 4) Structural unit produced from 2,6-dihydroxynaphthalene and terephthalic acid, 5) Bisphenol A and terephthalic acid A structural unit generated from an acid and the like can be mentioned.

[0018]

[Chemical 7]

The component (B) of the present invention is produced from other aromatic dicarboxylic acids, aromatic diols and aromatic hydroxycarboxylic acids, if necessary, in a small amount so as not to impair the object of the present invention. Structural units can be introduced. The temperature at which the component (B) of the present invention starts to show a liquid crystal state at the time of melting (hereinafter referred to as liquid crystal starting temperature) is preferably 150 to 350 ° C., more preferably 180 to 320.
C., particularly preferably 200 to 300.degree. 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 (ASTM) of the component (B) of the present invention
According to D648, 1/8 "thickness x 1/2" width x 5 "length,
A load of 18.6 kg / cm ² ) is preferably 130 to 3
The temperature is 00 ° C, more preferably 150 to 280 ° C, and particularly preferably 170 to 250 ° C. 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. Also,
By setting the heat distortion temperature to 130 to 210 ° C., fluidity,
The resin composition has relatively good molding processability, boss cracking, and hinge characteristics. Moreover, the heat distortion temperature is set to 210 to 300.
By setting the temperature to ℃, the obtained resin composition can have relatively good creep resistance and rigidity at high temperature, and the molding cycle in injection molding can be relatively shortened. 25 of the component (B) of the present invention
The loss tangent (tan δ) at ℃ is preferably 0.0
3 to 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 /
Second) is preferably 100 to 30,000 poise, more preferably 100 to 20,000 poise, and particularly preferably 100 to 10,000 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,
Particularly preferably, it is 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 resulting composition can be relatively shortened. The amount of component (B) used in the present invention is 1
-50% by weight, preferably 5-45% by weight, more preferably 10-40% by weight, particularly preferably 10-30% 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 halogen-based flame retardant of the component (C) used in the present invention is a halogenated epoxy compound such as halogenated epoxy oligomer or halogenated epoxy polymer represented by the general formula (f) chemical formula 8, tetrabromobisphenol A. , Tetrabromobisphenol A-bis (2
-Hydroxyethyl ether), tetrabromobisphenol A-bis (2,3-dibromopropyl ether)
Tetrabromobisphenol A derivative such as, tetrabromobisphenol A polycarbonate oligomer,
Halogenated polycarbonate oligomers such as polycarbonate oligomers of tetrabromobisphenol A and bisphenol A, polycarbonate oligomers of tetrabromobisphenol S, polycarbonate oligomers of tetrabromobisphenol S and bisphenol S, hexabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether,
Examples thereof include halogenated phenyl ether compounds such as poly (dibromophenylene ether) and bis (tribromophenoxy) ethane, and halogenated styrene compounds such as poly (dibromostyrene) and poly (tribromostyrene).

[0021]

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In the halogenated epoxy compound, the softening point is preferably 112 to 123 ° C., more preferably 112 to 250 ° C., and the weight average molecular weight is preferably 500.
To 30,000, more preferably 500 to 20,000
0, particularly preferably 1,000 to 10,000, having a bromine atom and / or chlorine atom content of 45 to 60% by weight,
The halogen-containing compound is preferably 47 to 58% by weight, and preferably R ¹ and R ² in the general formula (f) are represented by the general formula (g).

[0023]

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And X and Y are bromine atoms. For a general description of the halogenated epoxy compound represented by the above general formula (f), see JP-A-61-1
It is described in detail in Japanese Patent No. 241322 and the like. Among the known halogenated epoxy compounds, the flame retardancy excellent in heat resistance, practical moldability and impact resistance was obtained by specifying the softening point, weight average molecular weight, bromine atom and / or chlorine atom content. A resin composition can be obtained. If the softening point is less than 112 ° C, the desired heat resistance will not be obtained, while if it exceeds 250 ° C, the impact strength will decrease. If the weight average molecular weight is less than 500, the thermal stability during molding is poor, while if it exceeds 30,000, the dispersibility in the resin component is poor and the impact strength is reduced.
Furthermore, the bromine atom and / or chlorine atom content is 45
If it is less than wt%, it is necessary to increase the addition amount in order to obtain the desired flame retardancy, which inevitably reduces the impact strength,
On the other hand, when it exceeds 60% by weight, the thermal stability and light resistance during molding are deteriorated.

In the tetrabromobisphenol A derivative, tetrabromobisphenol A-bis (2-hydroxyethyl ether) and tetrabromobisphenol A-bis (2,3-dibromopropyl ether)
Is preferable, and tetrabromobisphenol A-bis (2-hydroxyethyl ether) is particularly preferable.
In the halogenated polycarbonate oligomer, the softening point is preferably 120 to 250 ° C, more preferably 150 to 200 ° C, and the weight average molecular weight is preferably 400.
~ 10,000, more preferably 450-8,000
0, particularly preferably 1,000 to 6,000, and a halogen-containing compound having a bromine atom and / or chlorine atom content of 45 to 70% by weight, preferably 50 to 60% by weight. In the halogenated phenyl ether compound, the softening point is preferably 100 to 320 ° C., more preferably 190 to 250 ° C., and the weight average molecular weight is preferably 400 to 10,000, more preferably 500 to
8,000, particularly preferably 600 to 7,000, bromine atom and / or chlorine atom content of 40 to 85% by weight, preferably 50 to 80% by weight, particularly preferably 60.
~ 75 wt% halogen-containing compound. Also,
In the halogenated styrene compound, the softening point is preferably 100 to 280 ° C, more preferably 130 to 26.
0 ° C., particularly preferably 140 to 250 ° C., the weight average molecular weight is preferably 1,000 to 100,000, more preferably 5,000 to 85,000, particularly preferably 7,000 to 85,000, a bromine atom and And / or a halogen-containing compound having a chlorine atom content of preferably 45 to 70% by weight, more preferably 50 to 70% by weight. By making these flame retardants within the above range,
A flame-retardant resin composition having particularly excellent flame retardancy, heat resistance, practical moldability, fluidity, impact resistance, boss strength, hinge characteristics, and weld strength can be obtained. Of these flame retardants, preferably halogenated epoxy compounds, halogenated polycarbonate oligomers, halogenated phenyl ether compounds, halogenated styrene compounds, more preferably halogenated polycarbonate oligomers, halogenated phenyl ether compounds, halogenated styrene compounds. Of these, halogenated phenyl ether compounds and halogenated styrene compounds are particularly preferable, and halogenated phenyl ether compounds are most preferable. Further, in the halogenated phenyl ether compound, poly (dibromophenylene ether) and bis (tribromophenoxy) ethane are preferable, and poly (dibromophenylene ether) is particularly preferable. Further, the halogenated styrene compound may be a polymer obtained by polymerizing a halogenated styrene monomer or a polymer obtained by halogenating a polymer of a styrene monomer.

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)
-50 parts by weight, preferably 5-40 parts by weight, particularly preferably 7-30 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 50 parts by weight, heat resistance, weld strength and impact resistance are poor, which is not preferable. In order to improve the flame retardant effect of the flame retardant (C), iron oxide, polytetrafluoroethylene and / or antimony-containing compound can be used.
The preferred amount of use for obtaining the effect of improving flame retardancy is 0.5 to 20 parts by weight, and more preferably 1 to 15 parts by weight, based on 100 parts by weight of all polymer components. The preferable weight average molecular weight of polytetrafluoroethylene is 500,000 to 50.
It is 0,000, and more preferably 1 to 3 million. Further, examples of the antimony-containing compound include antimony trioxide, antimony tetraoxide, (colloidal) antimony pentoxide, sodium antimonate, and antimony phosphate. Among them, antimony trioxide is preferable. If necessary, a flame retardant other than the component (C) can be used in an amount of less than 10 parts by weight. Preferably, an organic phosphorus compound is used as a flame retardant other than the component (C), and examples of the organic phosphorus compound include phosphates typified by triphenyl phosphate and phosphites typified by triphenyl phosphite. Examples thereof include the following general formulas 10 to 15
Is a compound having at least one structural unit represented by.

[0027]

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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. )

[0029]

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(In the formula, R _{1 to} R ₄ are each a hydrocarbon residue which may be substituted with halogen, R _{5 to} R ₈ are hydrogen atoms, halogen atoms or hydrocarbon residues, and X ^{1 to} X ⁸ are oxygen. Atom or sulfur atom, q _{1 to} q ₆ are 0 or 1, n
Indicates a number having a degree of polymerization of 1 to 30. )

[0031]

[Chemical 12]

(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. )

[0033]

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(Wherein 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 admixture of two or more. In the present invention, as the organic phosphorus compound, triphenyl phosphate, trithiophenyl phosphate represented by the following general formula 14, trixylenyl phosphate, trixylenyl phosphate represented by the following general formula 15, hydroquinone bis (diphenyl phosphate) , And resorcinol bis (diphenyl phosphate) are preferred.

[0036]

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[0037]

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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 flakes, glass beads, wollastonite, rock filler, calcium carbonate, talc, mica, glass flakes, milled fiber, kaolin, barium sulfate,
Fillers such as graphite, molybdenum disulfide, magnesium oxide, zinc oxide whiskers and potassium titanate whiskers can be used alone or in combination. Of these fillers, the shapes of glass fiber and carbon fiber are:
A fiber having a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more is preferable. These fillers are used in the composition 1 of the present invention.
It is usually used in the range of 5 to 150 parts by weight with respect to 00 parts by weight. Further, the composition of the present invention includes known coupling agents, light stabilizers, antioxidants, plasticizers, colorants, lubricants,
Additives such as antistatic agents, silicone oils, and foaming agents can be added. Further, by adding an antibacterial agent such as silver or a silver compound or a commercially available antifungal agent to the composition of the present invention, excellent antibacterial and antifungal properties can be imparted. The amount of such an antibacterial agent and antifungal agent is 0.0
It is 1 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 multi-phase structure polymer, if necessary. 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 the amount used is less than 0.5 parts by weight, the effect due to the addition of the multi-phase structure polymer will not be exhibited, and if it exceeds 40 parts by weight, heat resistance, fluidity, weld strength, rigidity, etc. will decrease, 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.

[0041]

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 / cm^TwoFlow 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 / cm^Two 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) -8 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, (A) -4, (A) -8
In emulsion polymerization, (A) -5, (A) -6, and (A) -7 were dissolved.
Obtained by liquid polymerization. 3. Polyamide 4,6: (A) -9 to (A) -11 (A) -9: DSM, Netherlands, Relative viscosity 2.2 (A) -10: DSM, Netherlands, Relative viscosity 3.0 (A) -11: DSM, Netherlands, relative viscosity 4.5Thermotropic liquid crystal polyester (B) -1 to (B)
-7 In a nitrogen atmosphere, p-hydroxybenzoic acid, 2-
Hydroxy-6-naphthoic acid and diol, dicarbo
By heating and melting the acid component and polycondensing it,
Thermotropic Liquid Crystal Polyester with Structural Formula
Obtained. (B) -1

[0042]

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(B) -2

[0044]

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(B) -3

[0046]

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(B) -4

[0048]

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(B) -5

[0050]

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(B) -6

[0052]

[Chemical 21]

(B) -7

[0054]

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Halogen flame retardants (C) -1 to (C) -9 The following halogen flame retardants were used. (C) -1; Weight average molecular weight 1,600 obtained by polymerization of tetrabromobisphenol A and epichlorohydrin
Stuff. (C) -2; having a weight average molecular weight of 5,000 and obtained in the same manner as in (C) -1. (C) -3; tetrabromobisphenol A-bis (2
-Hydroxyethyl ether) (C) -4; a polycarbonate oligomer of tetrabromobisphenol A having a weight average molecular weight of 1,800. (C) -5: Poly (dibromophenylene ether) having a weight average molecular weight of 6,000 and a bromine content of 62%. (C) -6; bis (tribromophenoxy) ethane (C) -7; poly (dibromostyrene) having a weight average molecular weight of 10,000. (C) -8; poly (dibromostyrene) having a weight average molecular weight of 80,000. (C) -9; poly (tribromostyrene) having a weight average molecular weight of 10,000. Filler (D) -1, (D) -2 The following (D) -1, (D) -2 were used as the filler. (D) -1: Carbon fiber; Asahi Fiber Glass Co., Ltd.
A9000 (D) -2: Glass fiber; EC manufactured by Nippon Electric Glass Co., Ltd.
S-03-F34 multiphase structure polymer (E) -1 to (E) -5 multiphase structure polymer having the composition shown in Table 3 was used. When these were observed with a scanning electron microscope, it was found that spherical resins having a particle size of 0.3 to 0.4 μm were uniformly dispersed.

Examples 1 to 74, Comparative Examples 1 to 6 Using the formulation shown in Tables 4 to 7, melt kneading was performed using a vented twin-screw extruder to form pellets. 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 4 to 7. The flame-retardant resin compositions of Examples 1-74 are excellent in flame retardancy, heat resistance, fluidity, weld strength, and rigidity, and their balance is particularly excellent. On the other hand, in Comparative Example 1, the components (A) and (B) are out of the range of the present invention, and the weld strength is poor. In Comparative Example 2, the components (A) and (B) are out of the range of the present invention, and the heat resistance, fluidity and rigidity are poor.
In Comparative Example 3, the components (A) and (B) are out of the range of the present invention, and the weld strength is poor. Comparative Example 4 is (A)
The component and the component (B) are outside the scope of the present invention, and the weld strength is poor. In Comparative Example 5, the component (C) is out of the range of the present invention, and the flame retardancy is poor. In Comparative Example 6, the component (C) is out of the range of the present invention, and the heat resistance, fluidity and weld strength are poor.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

[Table 3]

[0060]

[Table 4]

[0061]

[Table 5]

[0062]

[Table 6]

[0063]

[Table 7]

[0064]

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.

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[Procedure amendment]

[Submission date] February 1, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction contents]

[0041]

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 heat distortion temperature (° C) according to ASTM D848
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) -8 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, (A) -4, (A) -8
In emulsion polymerization, (A) -5, (A) -6, and (A) -7 were dissolved.
Obtained by liquid polymerization. 3. Polyamide 4,6: (A) -9 to (A) -11 (A) -9: DSM, Netherlands, Relative viscosity 2.2 (A) -10: DSM, Netherlands, Relative viscosity 3.0 (A) -11: DSM, Netherlands, relative viscosity 4.5Thermotropic liquid crystal polyester (B) -1 to (B)
-7 In a nitrogen atmosphere, p-hydroxybenzoic acid, 2-
Hydroxy-6-naphthoic acid and diol, dicarbo
By heating and melting the acid component and polycondensing it,
Thermotropic Liquid Crystal Polyester with Structural Formula
Obtained. The composition ratio of each component represents a molar ratio. (B) -1

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Hisao Nagai 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside Nippon Synthetic 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 consisting of the following structural units (a) and (b) and, if necessary, (c) and / or (d), Embedded image Embedded image Embedded image A flame-retardant resin composition comprising 1 to 50 parts by weight of (C) a halogen-based flame retardant, based on 100 parts by weight of (A) + (B).