JPH10101946A - Thermoplastic resin composition and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition that is flame-retardant and improved in mechanical properties and moldability. SOLUTION: This composition contains 100 pts.wt. thermoplastic resin and 0.5-60 pts.wt. organic bromide comprising a mixture containing a polymer, an oligomer and optionally a monomer. The ratio of the polymer in the organic bromide to the total amount of the monomer and the oligomer is 65/35 to 98/2 by weight. This product is prepared by molding a liquid crystal resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant thermoplastic resin composition having excellent mechanical properties and moldability, and a molded article.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for higher performance of plastics, and many polymers having various new properties have been developed and put on the market. Polymers with new properties are being used as engineering plastics in various parts such as automobiles, electric / electronics, precision machines, and office machines. On the other hand, these industrial materials are strongly required to have fire safety, that is, flame retardancy, in addition to the general balance of chemical and physical properties.

[0003] Polymeric flame retardants are oligomers that become impurities,
Since the monomer has a low molecular weight and is inferior in heat resistance, gas generation at the time of compounding the resin or molding is feared. It was generally removed and supplied to the market as substantially free of monomers or oligomers. However,
When such a brominated flame retardant is used, the flame retardancy cannot be said to be sufficient. Even if the desired flame retardancy can be obtained by increasing the compounding amount, the mechanical properties are reduced, and the appearance of the molded article surface is poor. ,
There are problems such as decomposition during molding, and it is difficult to obtain a material that solves these problems especially for a material processed at a high temperature of 250 ° C. or higher.

For example, a liquid crystal polyester processed at a high temperature of 250.degree.
A melt anisotropic polyester obtained by copolymerizing an acyloxy aromatic carboxylic acid with a typical polyester obtained from an alkylene glycol and a dicarboxylic acid described in JP-A-18016 is particularly a thin molded product (less than 1/32 inch).
It was found that the flame retardancy was insufficient.

[0005]

SUMMARY OF THE INVENTION
As a result of adding various flame retardants to the melt anisotropic polyester described in -18016, it was found that although the flame retardancy was improved, the retention stability during molding was not always good.

[0006] The present invention solves the above-mentioned problems and provides flame retardancy,
It is an object to obtain a thermoplastic resin composition and a molded article excellent in mechanical properties and moldability in a balanced manner.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention.

[0008] That is, the present invention relates to a thermoplastic resin 100
A composition comprising 0.5 to 60 parts by weight of an organic bromide comprising a mixture containing a high molecular weight substance and an oligomer, and optionally further containing a monomer, based on the weight of the organic bromide. The ratio of the monomer (C) of the thermoplastic resin composition and the organic bromide in which the ratio of the molecular weight to its monomer and oligomer is 65/35 to 98/2 (weight ratio) is the sum of the high molecular weight, the oligomer and the monomer 0 to 15% by weight of the thermoplastic resin composition, wherein the high molecular weight of the organic bromide is obtained from poly (brominated styrene) and / or brominated (polystyrene) The composition, the thermoplastic resin composition wherein the minimum moldable temperature of the thermoplastic resin is 250 ° C. or higher, a liquid crystalline polyester in which the thermoplastic resin forms an anisotropic molten phase, and The thermoplastic resin composition is one or more liquid-crystalline resin selected from liquid crystalline polyester amide liquid crystal resin has the following (I), (II) and (IV)
Liquid crystalline polyester consisting of structural units of
The above liquid crystalline resin composition which is a liquid crystalline polyester comprising the structural units of (I), (II), (III) and (IV),

Embedded image (However, R1 in the formula is

Embedded image R2 represents one or more groups selected from

Embedded image Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom, and the structural units (II) and (II)
The sum of I) and the structural units (IV) are substantially equimolar. ) 100 parts by weight of thermoplastic resin and 30 more filler
The thermoplastic resin composition containing 0 parts by weight or less, a thermoplastic resin molded article obtained by molding the thermoplastic resin composition, and a small thermoplastic resin molded article obtained by molding the thermoplastic resin composition. It is.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic resin used in the present invention is a synthetic resin which exhibits fluidity when heated and can be molded by utilizing this. Specific examples thereof include, for example, polyester, liquid crystal polyester, polycarbonate, polyamide, polyoxymethylene, wholly aromatic polyamide, wholly aromatic polyester, polyimide, polybenzimidazole, polyketone, polyetheretherketone, polyetherketone, polyether. Sulfone, polyphenylene oxide, phenoxy resin, polyphenylene sulfide, phenol resin, phenol-formaldehyde resin, olefin polymers such as polypropylene, polyethylene, polystyrene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / Non-conjugated diene copolymer, ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / methacrylic Glycidyl acid copolymer, ethylene / propylene-g-maleic anhydride copolymer, olefin copolymer such as ABS, and one or more mixtures selected from elastomers such as polyester polyether elastomer and polyester polyester elastomer Is mentioned. Further, specific examples of the polyester resin include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, polybutylene naphthalate, poly-1,4-cyclohexylene dimethylene terephthalate, and polyethylene-1,2-bis ( Phenoxy) ethane-4,4'-
In addition to dicarboxylate and the like, copolymerized polyesters such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / decanedicarboxylate and polycyclohexane dimethylene terephthalate / isophthalate are exemplified. Specific examples of the polyamide include a ring-opening polymer of a cyclic lactam, a polycondensate of an aminocarboxylic acid, and a polycondensate of a dicarboxylic acid and a diamine.
6, Nylon 6, 6, Nylon 6, 10, Nylon 6
Aliphatic polyamides such as 12, nylon 11, nylon 12, poly (meta-xylene adipamide), poly (hexamethylene terephthalamide), poly (hexamethylene isophthalamide), poly (tetramethylene isophthalamide), poly (methyl) Aliphatic-aromatic polyamides such as pentamethylene terephthalamide) and copolymers and mixtures thereof, for example, nylon 6 / hexamethylene terephthalamide, nylon 66 / hexamethylene terephthalamide, hexamethylene isophthalamide /
Examples thereof include hexamethylene terephthalamide, nylon 6 / hexamethylene isophthalamide / hexamethylene terephthalamide, and methylpentamethylene terephthalamide / hexamethylene terephthalamide.

Among these, polyesters such as polybutylene terephthalate, polybutylene naphthalate, poly-1,4-cyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalate and polyethylene terephthalate, from the viewpoints of mechanical properties and moldability. Nylon 6, Nylon 6.6, Nylon 4.6, Nylon 6 / Hexamethylene terephthalamide, Nylon 66 /
Polyamides such as hexamethylene terephthalamide, hexamethylene isophthalamide / hexamethylene terephthalamide, nylon 6 / hexamethylene isophthalamide / hexamethylene terephthalamide, methylpentamethylene terephthalamide / hexamethylene terephthalamide, liquid crystalline polyesters, liquid crystalline polyester amides , Polycarbonate, polyphenylene sulfide, polyethylene, polypropylene, polystyrene, ABS,
One or a mixture of two or more selected from polyphenylene oxide, phenoxy resin, phenol resin, and phenol-formaldehyde resin is preferable, and polybutylene terephthalate, polyethylene terephthalate, nylon 6, nylon 6.6, and nylon 4.
6, nylon 6 / hexamethylene terephthalamide, nylon 66 / hexamethylene terephthalamide, hexamethylene isophthalamide / hexamethylene terephthalamide, nylon 6 / hexamethylene isophthalamide / hexamethylene terephthalamide, methylpentamethylene terephthalamide / hexamethylene terephthalamide Amide, liquid crystalline polyester, liquid crystalline polyester amide,
Polycarbonate, polyphenylene sulfide, AB
One or two selected from S and polyphenylene oxide
A mixture of more than one species. In particular, when the minimum moldable temperature of the thermoplastic resin is 250 ° C. or higher, a material having a balance between flame retardancy and mechanical properties is obtained. Preferred examples of such a resin include polyethylene terephthalate,
Nylon 6.6, nylon 4.6, nylon 6 / hexamethylene terephthalamide, nylon 66 / hexamethylene terephthalamide, hexamethylene isophthalamide / hexamethylene terephthalamide, nylon 6 / hexamethylene isophthalamide / hexamethylene terephthalamide, methyl Pentamethylene terephthalamide /
Hexamethylene terephthalamide, liquid crystalline polyester, liquid crystalline polyester amide, polycarbonate, polyphenylene sulfide, polyphenylene oxide and the like can be mentioned, and these can be used as a mixture of two or more kinds. Further, when a liquid crystalline resin such as a liquid crystalline polyester and a liquid crystalline polyester amide having a relatively high processing temperature is used, there is almost no decrease in mechanical physical properties, and the most advantageous effects such as good flame retardancy can be obtained.

The minimum moldable temperature of a thermoplastic resin is the lowest temperature at which a thermoplastic resin can be melt-molded. Usually, the melting point is + 10 ° C., and those having no melting point are glass transition temperature + 100 ° C. Those having a liquid crystal onset temperature at a lower temperature can be molded if the liquid crystal onset temperature is attained.

The liquid crystalline polyester and the liquid crystalline polyesteramide which form the anisotropic molten phase in the liquid crystalline resin used in the present invention are aromatic oxycarbonyl unit, aromatic dioxy unit, aromatic dicarbonyl unit, ethylenedioxy A liquid crystalline polyester forming an anisotropic molten phase consisting of structural units selected from units and the like, and also selected from the above structural units and aromatic iminocarbonyl units, aromatic diimino units, aromatic iminooxy units, etc. It is a liquid crystalline polyesteramide that forms an anisotropic molten phase composed of structural units.

As an example of the liquid crystalline polyester forming the anisotropic molten phase, the liquid crystalline polyester preferably forming the anisotropic molten phase comprising the structural unit of the following structural unit (I) or the following structural unit (I) , A liquid crystalline polyester forming an anisotropic molten phase composed of the structural units of (II) and (IV), an anisotropic composed of the structural units of the following structural units (I), (II), (III) and (IV) And a liquid crystalline polyester forming an anisotropic molten phase comprising the structural units of the following structural units (I), (III) and (IV).

[0014]

Embedded image (However, R1 in the formula is

Embedded image R2 represents one or more groups selected from

Embedded image Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom, and the structural units (II) and (II)
The sum of I) and the structural units (IV) are substantially equimolar. ) The structural unit (I) is p-hydroxybenzoic acid, 2,6
A structural unit of a polyester formed from -hydroxynaphthoic acid, wherein the structural unit (II) is 4,4'-dihydroxybiphenyl, 3,3 ', 5,5'-tetramethyl-
4,4′-dihydroxybiphenyl, hydroquinone,
t-butylhydroquinone, phenylhydroquinone,
The structural unit formed from an aromatic dihydroxy compound selected from 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane, and 4,4′-dihydroxydiphenyl ether has the structure The unit (III) is a structural unit formed from ethylene glycol, and the structural unit (IV) is terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy ) Ethane-4,4′-dicarboxylic acid, 1,
2-bis (2-chlorophenoxy) ethane-4,4'-
The structural units generated from aromatic dicarboxylic acids selected from dicarboxylic acids and 4,4′-diphenyl ether dicarboxylic acids are shown below.

Examples of the liquid crystalline polyesteramide include 6-hydroxy-2-naphthoic acid, liquid crystalline polyesteramide formed from p-aminophenol and terephthalic acid, p-hydroxybenzoic acid, and 4,4′-dihydroxy acid. Liquid crystalline polyesteramide formed from biphenyl and terephthalic acid, p-aminobenzoic acid and polyethylene terephthalate (Japanese Patent Application Laid-Open No. 64-33123)
And the like.

The liquid crystalline polyester which can be more preferably used in the present invention is a copolymer comprising the above structural units (I), (II) and (IV), or the above structural units (I), (II) and (III) ) And (IV), and the copolymerization amount of the structural units (I), (II), (III) and (IV) is arbitrary. However, the following copolymerization amount is preferred from the viewpoint of fluidity.

That is, when the above structural unit (III) is contained, the total of the above structural units (I) and (II) is (I), (II) and (I) in view of heat resistance, flame retardancy and mechanical properties.
It is preferably from 60 to 95 mol% based on the total of (III),
5 to 93 mol% is more preferable. Also, the structural unit (III)
Represents 40 to 40 of the total of the structural units (I), (II) and (III).
5 mol% is preferable, and 25 to 7 mol% is more preferable.
Further, the molar ratio of the structural units (I) and (II) [(I) / (I
I)] is preferably 75/25 to 95/5 from the viewpoint of the balance between heat resistance and fluidity, and more preferably 78/2.
2 to 93/7. The structural unit (IV) is substantially equimolar to the sum of the structural units (II) and (III).

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

In the polycondensation of the liquid crystalline polyester which can be preferably used in the present invention, in addition to the components constituting the above structural units (I) to (IV), 3,3'-diphenyldicarboxylic acid, 2,2 Aromatic dicarboxylic acids such as' -diphenyldicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecandioic acid; alicyclic dicarboxylic acids such as hexahydroterephthalic acid; chlorohydroquinone, methylhydroquinone, 4,4'-dihydroxydiphenyl sulfone, 4,
4'-dihydroxydiphenyl sulfide, 4,4'-
Aromatic diols such as dihydroxybenzophenone,
Aliphatics such as 4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol;
Alicyclic diols and m-hydroxybenzoic acid, 2,6
Aromatic hydroxycarboxylic acids such as -hydroxynaphthoic acid and p-aminophenol, p-aminobenzoic acid and the like can be further copolymerized in a small proportion that does not impair the object of the present invention.

The method for producing a liquid crystalline resin according to the present invention comprises:
There is no particular limitation, and it can be produced according to a known polyester polycondensation method.

The organic bromide used in the present invention is an organic bromide comprising a mixture containing a high molecular weight substance and an oligomer, and optionally further containing a monomer. In the present invention, the high molecular weight usually refers to a tetramer or more, and the oligomer generally refers to a less than super monomeric tetramer,
Monomers usually refer to monomers.

The monomers, oligomers and high molecular weights constituting the organic bromide include organic bromine compounds usually used as flame retardants, and those having a bromine content of 20% by weight or more are particularly preferred. Specific examples include hexabromobenzene, pentabromotoluene, hexabromobiphenyl,
Monomeric organic bromine compounds such as decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromophenoxy) ethane, ethylene-bis (tetrabromophthalimide), and tetrabromobisphenol A; Brominated polycarbonates (for example, polycarbonate oligomers produced from brominated bisphenol A or copolymers thereof with bisphenol A), brominated epoxy compounds (for example, diepoxy compounds produced by the reaction of brominated bisphenol A with epichlorohydrin, Monoepoxy compounds obtained by the reaction of brominated phenols with epichlorohydrin), poly (brominated benzyl acrylate), bromine Polyphenylene ether, brominated bisphenol A, condensate of cyanuric chloride and brominated phenol, brominated (polystyrene), poly (brominated styrene), brominated polystyrene such as cross-linked brominated polystyrene, cross-linked or non-cross-linked brominated poly α- Examples include a polymer organic bromine compound such as a halogenated polymer such as methylstyrene, and the weight average molecular weight of such a polymer organic bromine compound is usually 1,000 to 1.5 million,
In particular, those having 5000 to 150,000 are preferably used, and those having 10,000 to 100,000 are more preferably used.

Among them, ethylene bis (tetrabromophthalimide), brominated epoxy polymer, brominated polystyrene, cross-linked brominated polystyrene, brominated polyphenylene ether and brominated polycarbonate are preferred, and brominated polystyrene is most preferably used.

The preferred polymer organic bromine compound will be described in more detail. As the brominated epoxy polymer, those represented by the following general formula (i) are preferred.

[0025]

Embedded image (In the above general formula, n represents the degree of polymerization of the repeating unit represented by ().) The weight average molecular weight in the above general formula (i) is from 1000 to 10
Preferably it is 100,000, particularly preferably 10,000 to 150,000.

As the brominated polystyrene used in the present invention, brominated (polystyrene) and cross-linked brominated polystyrene produced by brominating polystyrene obtained by radical polymerization or anionic polymerization, or radical polymerization of brominated styrene monomer Or produced by anionic polymerization, preferably radical polymerization
(ii) and / or (iii) poly (brominated styrene) having a brominated styrene unit represented by the formula.
The weight average molecular weight containing the structural unit represented by formula (ii) and / or (iii) as a main component is 1 × 10 ^{3 to} 120 × 1.
0 ⁴ poly (brominated styrene) is preferred.

[0027]

Embedded image The brominated styrene monomer as used herein is preferably a styrene monomer in which two to three bromine atoms have been introduced into the aromatic ring by a substitution reaction, and other than dibrominated styrene and / or tribrominated styrene. May contain monobrominated styrene.

The above-mentioned poly (brominated styrene) contains 60% by weight of dibrominated styrene and / or tribrominated styrene units.
Those containing at least 70% by weight are more preferable. In addition to dibrominated styrene and / or tribrominated styrene, poly (brominated styrene) obtained by copolymerizing 40% by weight or less, preferably 30% by weight or less of monobrominated styrene may be used. The weight average molecular weight of this poly (brominated styrene) is 1 × 10 ⁴ to 15 × 10
⁴ is more preferred.

As the cross-linked brominated polystyrene, polystyrene obtained by brominating porous polystyrene cross-linked with divinylbenzene is preferable.

As the brominated polycarbonate, those represented by the following general formula (iv) are preferred.

[0031]

Embedded image (R4 and R5 each represent a substituted or unsubstituted aryl group, most preferably a pt-butylphenyl group. In the above general formula, n represents the degree of polymerization of the repeating unit represented by ().) The weight average molecular weight in the formula (iv) is 1000 to 10
It is preferably 0,000, particularly preferably 5,000 to 150,000.

The weight-average molecular weight is calculated from Waters
Using a gel permeation chromatograph, column KD-80M /
Using KD-80M, add 0.02 to N-methylpyrrolidone.
The value measured at a flow rate of 0.5 ml / min using a solution of N lithium chloride dissolved as a developing solvent, a detector of UV (260 nm), and a sample concentration of 1 mg / ml. The relative value is based on polystyrene molecular weight. -Methylpyrrolidone, which is difficult to measure, may be measured using a solvent that dissolves the analyte, such as tetrahydrofuran, instead.

The above-mentioned polymer-based organic bromine compound can be usually produced by polymerizing an unbrominated monomer and then brominating the resulting polymer-based organic bromine compound. It has a distribution, and in many cases, the content of oligomers and monomers is extremely small.
It can also be produced by polymerizing a brominated monomer, and the resulting polymer organic bromine compound is
It usually has a molecular weight distribution, and usually contains a high molecular weight substance, an oligomer, and in some cases, a mixture further containing a monomer. In addition, the ratio of each component usually depends on the polymerization conditions such as the degree of polymerization or the polymerization time.

The high molecular weight, oligomer, and monomer of these organic bromides can be distinguished from each other by determining the degree of polymerization from the molecular weight calculated by gel permeation chromatography. Good, degree of polymerization is more than 1 4
Those having a degree of polymerization of less than 1 are oligomers and those having a degree of polymerization of 1 or less are monomers.

The organic bromide used in the present invention contains a high molecular weight substance and an oligomer in a specific ratio, and may further contain a monomer in some cases, but the mixing ratio is determined by the sum of polymer / monomer and oligomer. = 65 / 35-
98/2 (weight ratio), preferably 70/30 to 98/2
(Weight ratio), more preferably 80/20 to 95/5 (weight ratio).

The proportion of the organic bromide monomer (C) is
0 based on the sum of the high molecular weight, oligomer and monomer
It is preferably from 15 to 15% by weight, particularly preferably from 0 to 10% by weight.

The ratio of the high polymer / oligomer / monomer can be determined by, for example, using a Waters gel permeation chromatograph using a column KD-80M / KD-80M,
It can be determined by measuring the peak area ratio at a flow rate of 0.5 ml / min, detector: UV (260 nm), and sample concentration of 1 mg / ml, using 0.02N lithium chloride dissolved in methylpyrrolidone as a developing solvent. . If N-methylpyrrolidone is difficult to measure, it may be measured using tetrahydrofuran instead.

In the present invention, the above-mentioned polymer organic bromine compound is used alone, and the degree of polymerization, polymerization time, polymerization temperature and the like are appropriately adjusted so that the proportion of high molecular weight, monomer and oligomer is within the above range. , Or may be prepared by blending an oligomer or a monomeric organic bromine compound with a polymer organic bromine compound having a high molecular weight as a main component so as to be within the above range, or treating the polymer. The amount of the monomer or oligomer may be adjusted to fall within the above range.

In the present invention, the following methods may be mentioned as specific examples for controlling the high molecular weight, monomer and oligomer of the organic bromide within the above range.

That is, most of brominated products produced by brominating polystyrene obtained by radical polymerization or anionic polymerization are usually high-molecular-weight products. It is prepared so as to be in the composition range. In addition, the amount of the bromide obtained by polymerizing the organic brominated monomer varies depending on the polymerization conditions such as the polymerization time and the degree of polymerization. A heat treatment under a vacuum of ~ 250 ° C for 1 to 10 hours, and a de-oligomerization and de-monomerization treatment, or a Soxhlet extraction with an organic solvent such as acetone or methanol for about 1 to 2 hours.
A method of dissolving in a soluble solvent such as methylpyrrolidone and reprecipitating with a poor solvent is preferably used.

In the present invention, such an organic bromide,
That is, by using an organic bromide in which a high molecular weight substance and an oligomer (and, in some cases, a monomer) are present at a specific ratio, flame retardancy, retention stability, and product appearance are balanced at a high level.

In particular, the presence of low molecular weight compounds, especially oligomers, in the organic bromide containing high molecular weight compounds affects the flame retardancy of the resulting composition, especially in thin molded articles.

The amount of the organic bromide is preferably 0.5 to 60 parts by weight, more preferably 1 to 40 parts by weight, per 100 parts by weight of the thermoplastic resin.

In the liquid crystalline resin composition of the present invention, the organic bromide is preferably dispersed in the composition at an average diameter of 25 μm or less, more preferably at 2.0 μm or less.

In the present invention, a filler can be used for imparting mechanical strength and other properties of the thermoplastic resin. The filler is not particularly limited, but may be a fibrous, plate-like, powder-like, or granular-like material. Fillers such as can be used. Specifically, for example, glass fiber, PAN-based or pitch-based carbon fiber, stainless fiber, metal fiber such as aluminum fiber or brass fiber, organic fiber such as aromatic polyamide fiber, gypsum fiber, ceramic fiber, asbestos fiber,
Fibrous such as zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, whisker-like filler, mica, talc , Kaolin,
Examples of the filler include powdery, granular, and plate-like fillers such as silica, calcium carbonate, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, walasteinite, titanium oxide, zinc oxide, calcium polyphosphate, and graphite. Among the above fillers, glass fibers are preferably used. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and for example, it can be selected from long fiber type or short fiber type chopped strand, milled fiber and the like.
Further, two or more of the above fillers can be used in combination. The filler used in the present invention may be used after its surface is treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, or the like) or another surface treatment agent. .

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

The amount of the above filler is 10
300 parts by weight or less with respect to 0 parts by weight, preferably 1 part by weight.
0 to 250 parts by weight, more preferably 20 to 150 parts by weight.

Further, the thermoplastic resin composition of the present invention contains an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites and the like) and an ultraviolet absorber (for example, resorcinol, salicylate, Benzotriazole, benzophenone, etc.), lubricants and release agents (montanic acid and its salts, its esters, its half esters, stearyl alcohol, stearamide and polyethylene wax, etc.),
Colorants including dyes (eg, nigrosine) and pigments (eg, cadmium sulfide, phthalocyanine, etc.),
Ordinary additives such as crystal nucleating agents, plasticizers, flame retardant aids (antimony compounds such as antimony oxide and sodium antimonate, zirconium oxide, zinc sulfide, barium sulfate, etc.), and other additives such as antistatic agents and other thermoplastic resins ( Fluororesin or the like) can be added to impart predetermined characteristics.

The method for producing the thermoplastic resin composition and the molded article of the present invention is not particularly limited, but is preferably produced by melt-kneading, and a known method can be used for melt-kneading. For example, using a Banbury mixer, a rubber roll machine, a kneader, a single-screw or twin-screw extruder, or the like, melt kneading at a temperature of 200 to 400 ° C. to form a composition, and injecting the thus obtained thermoplastic resin composition of the present invention. Molding, extrusion molding, blow molding, and other ordinary molding methods include methods for forming molded articles, and these methods can be processed into molded articles such as three-dimensional molded articles, sheets, and container pipes. .

Further, a method in which a master pellet containing the organic bromide used in the present invention at a high concentration is prepared, and the master pellet is mixed with a pellet for dilution at the time of molding, and then molded is preferably used. The composition and the molded product thus obtained have excellent corrosion resistance, moldability, mechanical properties, and surface appearance, and make use of these properties, for example, various gears, various cases, sensors, LEP lamps, connectors, Socket, resistor, relay case switch coil bobbin, condenser, variable condenser case, optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, microphone, headphones, small motor, magnetic head base, power Modules, housings, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, electrical and electronic parts such as computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, electronics range Goods,
Audio parts, audio equipment parts such as audio laser discs and compact discs, lighting parts, refrigerator parts,
Air conditioner parts, typewriter parts, word processor parts, and other household and office electrical product parts, office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, oilless bearings, stern bearings, Various bearings such as underwater bearings, motor parts, mechanical parts such as lighters, typewriters, etc., optical equipment such as microscopes, binoculars, cameras, watches, etc., precision mechanical parts; alternator terminals, alternator connectors, IC regulator, potentiometer base for light deer, various valves such as exhaust gas valve, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel,
Intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake butt Wear sensor, thermostat base for air conditioner, heating and hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related components, dust switcher, starter switch, starter relay, wire harness for transmission, window Osher nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, For automotive and vehicle related parts such as fuse connectors, horn terminals, electrical component insulation plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, and other various applications Useful, especially 50m volume
It is useful for small molded products having a thickness of 1 or less or molded products having a thin portion.

[0051]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the invention.

Reference Example 1 The thermoplastic resin used in the present invention is shown below.

LCP1: liquid crystal polyester (liquid crystal onset temperature: 293 ° C.) (994 parts by weight of p-hydroxybenzoic acid, 126 parts by weight of 4,4′-dihydroxybiphenyl)
Polymerization was carried out in a pressure vessel with 112 parts by weight of terephthalic acid, 216 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 960 parts by weight of acetic anhydride, and pellets were obtained by a conventional method. N66: Nylon 66 (melting point 265 ° C) (CM3001N)
(Manufactured by Toray Industries, Inc.) N46: Nylon 46 (melting point: 290 ° C.) (F5000: Unitika Ltd.) PET: polyethylene terephthalate (melting point: 255 ° C.)
(T9OOE (manufactured by Toray Industries, Inc.)) PC: polycarbonate (glass transition temperature 150 ° C)
(Iupilon S-3000 (Mitsubishi Enplastics Corporation)
Reference Example 2 The flame retardants used in the present invention are shown below.

1. Poly (brominated styrene) (high molecular weight / oligomer / monomer = 85/12/3 wt%, bromination ratio 68%, weight average molecular weight: about 25,000): poly (brominated styrene) obtained from tribrominated styrene A poly (brominated styrene) containing 65 wt% of a high molecular weight substance, 20 wt% of an oligomer, and 15 wt% of a monomer is 5 mmH
g at 180 ° C. for 4 hours under reduced pressure.

2. Poly (brominated styrene) (high molecular weight / oligomer / monomer = 90/8/2 wt%, bromination ratio 68%, weight average molecular weight: about 27000): poly (brominated styrene) obtained from tribrominated styrene A poly (brominated styrene) containing 65 wt% of a high molecular weight substance, 20 wt% of an oligomer, and 15 wt% of a monomer is 5 mmH
g at 180 ° C. for 4.5 hours under reduced pressure.

3. Poly (brominated styrene) (high molecular weight / oligomer / monomer = 82/13/5 wt%, bromination ratio 68%, weight average molecular weight: about 25,000): poly (brominated styrene) obtained from tribrominated styrene A poly (brominated styrene) containing 65 wt% of a high molecular weight substance, 20 wt% of an oligomer, and 15 wt% of a monomer is 5 mmH
g at 180 ° C. for 3 hours under reduced pressure.

4. Poly (brominated styrene) (high molecular weight / oligomer / monomer = 50/28/22 wt%, bromination ratio 67%, weight average molecular weight: about 23000): poly (brominated styrene) obtained from tribrominated styrene 65% by weight of a high molecular weight substance, 20% by weight of an oligomer,
Poly (brominated styrene) 1000 with 15 wt% monomer
to 300 g of a mixture of dibrominated styrene and a monomer of styrene and a dimer or trimer of dibrominated styrene were added in an amount of 300 g.

5. Poly (brominated styrene) (high molecular weight / oligomer / monomer = 99 / 0.5 / 0.5wt)
%, Bromination rate 67%, weight average molecular weight: about 3000
0): Poly (brominated styrene) obtained from 3-brominated styrene, which is 65% by weight of a high molecular weight substance and oligomer 2
Poly (brominated styrene) containing 0 wt% and 15 wt% of monomer was dissolved in N-methyl-2-pyrrolidone and reprecipitated with methanol.

Each evaluation was measured according to the method described below.

6. Brominated polycarbonate (high molecular weight / oligomer, monomer = 87/1/12 wt%):
(Dai Nippon Ink Co., Ltd. “Platherm” EXP030
(High molecular weight / oligomer, monomer = 98.2 / 1 /
(0.8% by weight) 140 g of brominated bisphenol A was additionally added to 1000 g.

7. Brominated polycarbonate (high molecular weight / oligomer, monomer = 60.2 / 1 / 38.8wt)
%): (Dai Nippon Ink Co., Ltd. "Platherm" EXP
030 (high molecular weight / oligomer, monomer = 98.2)
(1/1 / 0.8 wt%) was obtained by adding 660 g of brominated bisphenol A to 1000 g.

(1) Retention stability The AS was obtained under two conditions in which the molding retention time was changed to 4 minutes and 20 minutes.
A TM1 tensile test piece was molded, the tensile strength was measured, and the tensile strength at a molding residence time of 20 minutes / tensile strength at a molding residence time of 4 minutes × 100 was determined as the tensile strength retention.

(2) Molded article blister test Twenty molded articles of 12 × 80 × 3 mm were molded at a filling time of 0.15 mm / s and a minimum filling pressure of +0.1 MPa, and the number of molded articles swollen by gas was determined. .

(3) Flame Retardancy A 1 / 64-inch thick combustion test piece was injection molded and subjected to UL9
A vertical combustion test was performed according to the four standards.

Examples 1-5, Comparative Examples 1-4 Organic bromides and fillers were dry-blended with the thermoplastic resin shown in Reference Example 1 in the proportions shown in Table 1, and then 30 mmφ.
Pellets were obtained by melt-kneading with a twin-screw extruder. This pellet is then used for Sumitomo injection molding machine (Sumitomo Heavy Industries, Ltd.)
Was used to perform injection molding to obtain a test piece.

Table 1 shows the evaluation results. In addition, the cylinder temperature of the extruder at the time of melt-kneading with the twin-screw extruder and the cylinder temperature of the injection molding machine at the time of injection molding were the temperatures shown as molding processing temperatures in Table 1.

In the comparative example, a vertical combustion test was performed in the same manner as in Example 1 except that the thickness was changed to 1/32 inch, and the result was V-0. Similarly, the flame retardancy was measured to be V-2.

[0068]

[Table 1] From the results in Table 1, it is possible to obtain a molded article having excellent mechanical properties and moldability and good appearance while imparting flame retardancy by using a specific ratio of a high molecular weight substance, a monomer and an oligomer. be able to.

[0069]

The liquid crystalline resin composition and the molded article of the present invention are provided with flame retardancy and can easily obtain a molded article having excellent mechanical properties and good appearance. It is suitable for various other uses such as machine-related equipment, office equipment, and automobile / vehicle-related parts.

Claims (9)

[Claims] 1. A composition comprising 0.5 to 60 parts by weight of an organic bromide comprising a mixture containing a high molecular weight substance and an oligomer and optionally further containing a monomer, based on 100 parts by weight of a thermoplastic resin. A thermoplastic resin composition having a high molecular weight of the organic bromide and a total ratio of the monomer and the oligomer of 65/35 to 98/2 (weight ratio). 2. The ratio of the organic bromide monomer (C) is as follows:
0 based on the sum of the high molecular weight, oligomer and monomer
The thermoplastic resin composition according to claim 1, wherein the content is from 15 to 15% by weight. 3. The thermoplastic resin composition according to claim 1, wherein the organic bromide is poly (brominated styrene) and / or brominated (polystyrene). 4. The minimum moldable temperature of the thermoplastic resin is 250.
The thermoplastic resin composition according to any one of claims 1 to 3, wherein the temperature is at least 0C. 5. The liquid crystal display device according to claim 1, wherein the thermoplastic resin is at least one liquid crystal resin selected from liquid crystal polyesters and liquid crystal polyesteramides forming an anisotropic molten phase. Or a thermoplastic resin composition as described above. 6. A liquid crystalline polyester wherein the liquid crystalline resin comprises the following structural units (I), (II) and (IV), or the structural units of (I), (II), (III) and (IV) The liquid crystalline resin composition according to claim 5, which is a liquid crystalline polyester comprising: Embedded image (However, R1 in the formula is R2 represents one or more groups selected from Represents one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom, and the structural units (II) and (II)
The sum of I) and the structural units (IV) are substantially equimolar. ) 7. The composition according to claim 1, wherein the filler is further contained in an amount of not more than 300 parts by weight based on 100 parts by weight of the thermoplastic resin.
7. The thermoplastic resin composition according to any one of 6. 8. A thermoplastic resin molded article obtained by molding the thermoplastic resin composition according to claim 1. 9. A small-sized molded article of a thermoplastic resin obtained by molding the thermoplastic resin composition according to any one of claims 1 to 7.