JP2979646B2 - Flame retardant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for higher performance of plastics, and a number of polymers having various new properties have been developed and marketed. Among them, optics characterized by a parallel arrangement of molecular chains. Anisotropic liquid crystal polymers have attracted attention because of their excellent fluidity and mechanical properties.
However, what has been known as this liquid crystal polymer has a low deflection temperature under load and does not necessarily have sufficient heat resistance, or has good heat resistance, but cannot be molded unless the melting point is too high and 400 ° C. or higher. It has been difficult to obtain a polymer having a good balance between heat resistance and moldability.

On the other hand, it is known that many thermoplastic polymers are inferior in liquidity and mechanical properties at the time of molding and have insufficient heat resistance as compared with liquid crystal polymers.

[0004] Therefore, it has been proposed to add various liquid crystal polymers into a composition in order to improve the fluidity and mechanical properties of the thermoplastic polymer during molding (Japanese Patent Application Laid-Open No. 56-115357). JP, JP-A-57-51739, etc.).

[0005] Also, in general, liquid crystal polyester has flame resistance, and has a property of forming a carbonized layer by self-expanding when directly exposed to a flame.
ng magazine, February 1980, "Foaming fire protection paint: The most important defense method against fire" is known. However, it has been found that when the liquid crystal polyester and the thermoplastic resin are blended, the flame retardancy (particularly a thin molded product) is not sufficient when the blending ratio of the thermoplastic resin increases.

[0006]

[Problems to be Solved by the Invention]
No. 18016, a liquid crystal polymer described in
As a result of adding an organic bromine compound-based flame retardant and an antimony compound to a composition comprising a liquid crystal polymer and a thermoplastic polymer described in No. 7870, the effect of improving heat resistance is insufficient or the heating temperature during compounding is too high. The thermoplastic polymer and the flame retardant themselves decomposed, and it was found that there was a problem that a practical composition could not be obtained, that the mechanical properties were poor, and that the retention stability during molding was not always good. .

An object of the present invention is to solve the above-mentioned problems, and to provide a flame-retardant resin composition having excellent heat resistance, moldability and mechanical properties, and having good retention stability.

[0008]

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

That is, the present invention relates to (A) the following (I), (II), (IV) or (I), (II), (III)
, The deflection temperature under load comprising the structural unit of (IV) is 150 to
280 ° C thermotropic liquid crystal polyester 1-99
(B) polyamide, polyoxymethylene, polycarbonate, polyarylene oxide, semi-aromatic polyester, polyarylene sulfide, polysulfone, polyethersulfone, amorphous polyarylate, polyetheretherketone At least one thermoplastic resin 99 selected from
To 100 parts by weight of a resin composition consisting of

[0010]

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(Where R1 in the formula is

[0012]

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R2 represents one or more groups selected from

[0014]

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And represents one or more groups selected from Also,
In the formula, X represents a hydrogen atom or a chlorine atom, and the structural unit (II)
And total a structural unit (III) (IV) is substantially equimolar. ) (C) 0 to 200 parts by weight of a filler, and (D) polybrominated styrene having a weight average molecular weight of 1 × 10 ³ to 30 × 10 ⁴ containing the following structural units as main components produced from a brominated styrene monomer: And a flame-retardant resin composition containing 0.5 to 60 parts by weight and (E) 0 to 30 parts by weight of an antimony compound.

[0016]

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The present invention provides the flame-retardant resin composition as described above, wherein the thermotropic liquid crystal polyester (A) contains an ethylenedioxy unit as an essential component.

In the present invention, it is important to blend a specific polybrominated styrene produced from a brominated styrene monomer into a composition comprising a thermotropic liquid crystal polyester and a thermoplastic resin. Thus, a resin composition having excellent heat resistance, flame retardancy and mechanical properties can be obtained.

The structural unit (I) is a structural unit of a polyester formed from p-hydroxybenzoic acid, and the structural unit (II) is 4,4'-dihydroxybiphenyl, 3,3
', 5,5'-Tetramethyl-4,4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-
Bis (4-hydroxyphenyl) propane and 4,4
The structural unit generated from an aromatic dihydroxy compound selected from '-dihydroxydiphenyl ether, the structural unit (III) is a structural unit generated from ethylene glycol, and the structural unit (IV) is terephthalic acid, isophthalic acid,
4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,
The structural units generated from aromatic dicarboxylic acids selected from 4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid, and diphenyl ether dicarboxylic acid are respectively shown. In particular, when a structural unit (III) is contained, R1 is

[0020]

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Is at least 70 mol% of the structural unit (II), and R 2 is

[0022]

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Those which occupy at least 70 mol% of the structural unit (IV) are particularly preferred.

The thermotropic liquid crystalline polyester (A) used in the present invention is a copolymer comprising the above structural units (I), (II), (IV) or (I), (II), (III), (IV). It is united.

The structural units (I), (II), (III) and (I)
The copolymerization amount of V) is arbitrary. However, the following copolymerization amount is preferred from the viewpoint of fluidity.

That is, when the above-mentioned structural unit (III) is contained, the total of the above-mentioned structural units (I) and (II) is the sum of the structural units (I) and (II) from the viewpoint of heat resistance, flame retardancy and mechanical properties. )and
It is preferably from 60 to 95 mol% based on the total of (III) ,
2-93 mol% is more preferred. Also, the structural unit (III)
Represents 40 with respect to the sum of the structural units (I), (II) and (III).
５5 mol% is preferred, and 18-7 mol% is more preferred. Also, the molar ratio of the structural units (I) and (II) [(I) / (I
I)] is preferably 7 from the viewpoint of the balance between heat resistance and fluidity.
5/25 to 95/5, more preferably 78/22.
９３93/7. The structural unit (IV) is the structural unit (II)
And (III) are substantially equimolar.

On the other hand, if that does not contain the structural unit (III) Oyo the structural units from the viewpoint of fluidity (I) the structural unit (I)
And (II)], preferably from 40 to 90 mol%, particularly preferably from 60 to 88 mol%. The structural unit (IV) is substantially equimolar to the structural unit (II).

The thermotropic liquid crystal polyester (A) in the present invention has a deflection temperature under load of 150 to 280 ° C.
Is essential, and 190 to 280 ° C. is preferable.

If the deflection temperature under load is less than 150 ° C., the effect of improving heat resistance is insufficient. If it exceeds 280 ° C., the thermoplastic polymer is thermally decomposed at the time of compounding, and the molding temperature of the obtained resin composition becomes high. The problem occurs.

Here, the deflection temperature under load is ASTM D64.
8 and 1/8 "x 1/2" x 5 "
It is a value measured under a stress of 8.56 kgf / cm2.

The method for producing the thermotropic liquid crystal polyester (A) in the present invention is not particularly limited, and it can be produced according to a known polyester polycondensation method.

For example, when the above-mentioned structural unit (III) is not contained, the production methods (1) to (4) are preferable, and when the above-mentioned structural unit (III) is contained, the production method (5) is preferable.

(1) p-acetoxybenzoic acid and 4,
A method of producing a polyacylated aromatic dihydroxy compound such as 4'-diacetoxybiphenyl or paraacetoxybenzene from an aromatic dicarboxylic acid such as terephthalic acid by a deacetic acid polycondensation reaction.

(2) p-hydroxybenzoic acid and 4,
A method of reacting an aromatic dihydroxy compound such as 4'-dihydroxybiphenyl or hydroquinone, or an aromatic dicarboxylic acid such as terephthalic acid with acetic anhydride to acylate a phenolic hydroxyl group, followed by a deacetic acid polycondensation reaction.

(3) Manufactured by a dephenol polycondensation reaction from a phenyl ester of p-hydroxybenzoic acid or an aromatic dihydroxy compound such as 4,4'-dihydroxybiphenyl or hydroquinone with a diphenyl ester of an aromatic dicarboxylic acid such as terephthalic acid. how to.

(4) A desired amount of diphenyl carbonate is reacted with an aromatic dicarboxylic acid such as p-hydroxybenzoic acid and terephthalic acid to form a diphenyl ester, and then an aromatic such as 4,4'-dihydroxybiphenyl and hydroquinone. A method in which a dihydroxy compound is added and the product is produced by a dephenol polycondensation reaction.

(5) a polyester polymer from ethylene glycol and an aromatic dicarboxylic acid such as terephthalic acid,
A process according to (1) or (2) in the presence of a bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid such as an oligomer or bis (β-hydroxyethyl) terephthalate.

Typical catalysts used in the polycondensation reaction include metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate, antimony trioxide, magnesium and sodium acetate. It is effective for

Some of the thermotropic liquid crystal polyesters (A) used in the present invention can be measured for their logarithmic viscosity in pentafluorophenol. In this case, the concentration is 0.1 g / dl at 60 ° C. The measured value is preferably 0.5 or more, particularly preferably 1.0 to 3.0 dl / g when the above structural unit (III) is contained.
When (I) is not contained, the content is preferably 2.0 to 10.0 dl / g.

The thermotropic liquid crystal polyester (A) used in the present invention has a melt viscosity of 10 to 2,000.
0 poise is preferable, and 20 to 10,000 poise is particularly preferable.

The melt viscosity is determined by the structural unit (III)
Is included, the melting point (Tm) is + 10 ° C., and if the structural unit (III) is not included, the liquid crystal onset temperature is + 40 ° C.
Are values measured by a Koka type flow tester under the conditions of a shear rate of 1,000 (1 / sec).

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

The liquid crystal onset temperature is a temperature at which the polymer is heated and heated on a sample stage of a polarizing microscope and emits opalescent light under shear stress.

In the polycondensation of the thermotropic liquid crystal polyester used in the present invention, 3,3'-diphenyldicarboxylic acid, 2,2 'other than the components constituting the structural units (I) to (IV) are used. -Aromatic dicarboxylic acids such as diphenyldicarboxylic acid, adipic acid, azelaic acid, sebacic acid, aliphatic dicarboxylic acids such as dodecanedioic 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.

In the resin composition of the present invention, polyamide, polyoxymethylene, polycarbonate, polyarylene oxide, semi-aromatic polyester, polyarylene sulfide, polysulfone, polyethersulfone, amorphous polyarylate, polyetherether One or more thermoplastic resins (B) selected from ketones are essential components, and those having a deflection temperature under load of less than 190 ° C are preferable. .

Preferred specific examples of the thermoplastic resin (B) include the following.

As the polyamide, nylon 6, nylon 46, nylon 66, nylon 610, nylon 1
1, nylon 12, and the like, and copolymers thereof. Polyoxymethylene includes polyoxymethylene homopolymers and copolymers in which the main chain is largely composed of oxymethylene chains. Polycarbonates are based on hydrocarbon derivatives containing bis (4-hydroxyphenyl), bis (3,5-dialkyl-4-hydroxyphenyl) or bis (3,5-dihalo-4-hydroxyphenyl) substitution. Polycarbonates are preferred, and polycarbonates based on 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) are particularly preferred. Examples of polyarylene oxide include poly (2,6-dimethyl-1,4-phenylene) ether, 2,6-dimethylphenol / 2,
3,6-trimethylphenol copolymer, 2,6-dimethylphenol / 2,3,6-triethylphenol copolymer and the like can be mentioned.

Styrene resins such as polystyrene and high-impact polystyrene can be added to polyarylene oxide.

Examples of the semi-aromatic polyester include polyethylene terephthalate and polybutylene terephthalate. Examples of polyarylene sulfide include polyparaphenylene sulfide.

The polysulfone has the structural formula

[0051]

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And the like.

The polyether sulfone has the structural formula

[0054]

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And the like.

As the amorphous polyarylate, the structural formula

[0057]

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Or

[0059]

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And the like.

The polyetheretherketone has the structural formula

[0062]

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And the like.

As the thermoplastic resin (B) used in the present invention, among the above, polyamide, polycarbonate, semi-aromatic polyester, amorphous polyarylate and polyarylene sulfide can be particularly preferably used.

In the present invention, the amount of the thermotropic liquid crystal polyester (A) is 1 to 99% by weight, preferably 5 to 95% by weight, and the amount of the thermoplastic resin (B) is 9%.
It needs to be 9 to 1% by weight, preferably 95 to 5% by weight. If the amount of the thermotropic liquid crystal polyester (A) is less than 1% by weight, heat resistance, fluidity and mechanical properties are insufficient, and if it exceeds 99% by weight, anisotropy of mechanical properties becomes large.

In the present invention, it is possible to further improve the heat resistance by using the filler (C).
A molded product having an extremely high deflection temperature under load can be obtained.

(C) which can be used in the present invention
As fillers for the components, glass fiber, carbon fiber, aromatic polyamide fiber, potassium titanate fiber, gypsum fiber, brass fiber, stainless steel fiber, steel fiber, ceramic fiber, boron whisker fiber, mica, talc, silica,
Examples include fibrous, powdery, granular or plate-like inorganic fillers such as calcium carbonate, glass beads, glass flakes, glass microballoons, clay, wollastenite, and titanium oxide. Among the above fillers, glass fibers are preferably used. The type of the glass fiber is not particularly limited as long as it is generally used for reinforcing a resin. For example, a long fiber type or a short fiber type chopped strand, a milled fiber or the like can be used. Further, the glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer, a thermosetting resin such as an epoxy resin, or a coupling agent such as a silane-based or titanate-based resin, or the like. Surface treatment agent.

The amount of the filler (C) to be added is 200 parts by weight or less, more preferably 100 parts by weight, per 100 parts by weight of the composition comprising the thermotropic liquid crystal polyester (A) and the thermoplastic resin (B). Not more than parts by weight.

The polybrominated styrene (D) used as a flame retardant in the present invention is defined as a main component of the following structural unit produced from a brominated styrene monomer and having a weight average molecular weight of 1 × 10 ³ to 30 × 10 ^4. Is a polybrominated styrene.

[0070]

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The term "brominated styrene monomer" as used herein refers to a substance obtained by introducing about two bromine atoms into the aromatic of one styrene monomer by a substitution reaction. In addition to dibrominated styrene, monobrominated styrene is used. , Tribrominated styrene and the like.

The polybrominated styrene preferably contains at least 60% by weight of dibrominated styrene units.
Those containing 70% by weight or more are more preferable. In addition to dibrominated styrene, polybrominated styrene obtained by copolymerizing monobrominated styrene and / or tribrominated styrene to 40% by weight or less, preferably 30% by weight or less may be used.

The weight average molecular weight of the polybrominated styrene is more preferably from 1 × 10 ⁴ to 15 × 10 ⁴ . When the weight-average molecular weight is less than 1 × 10 ³ , the mechanical properties at the time of molding retention and the decrease in solder heat resistance are large, and when it is more than 30 × 10 ⁴ , the fluidity of the composition of the present invention becomes poor and any This is not preferred. Further, the polybrominated styrene is preferably dispersed in the composition of the present invention at an average diameter of 2.5 μm or less, more preferably at 2.0 μm or less.

This polybrominated styrene can also be produced by brominating polystyrene obtained by radical polymerization or anionic polymerization. However, the deterioration of the mechanical properties and the deterioration of the color at the time of molding retention are large, It is necessary to produce brominated styrene by radical or anionic polymerization, preferably by radical polymerization.

The weight average molecular weight is a value measured using a gel permeation chromatograph, and is a relative value based on polystyrene molecular weight.

The addition amount of the polybrominated styrene is 0.5 to 60 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the thermotropic liquid crystal polyester (A) and the thermoplastic resin (B) in total. Parts by weight, more preferably 2 to 15 parts by weight. If the amount is less than 0.5 part by weight, the flame-retardant effect is insufficient.
It is not preferable because thermal characteristics are deteriorated.

In the flame-retardant resin composition of the present invention, an antimony compound (E) may be added as a flame-retardant aid in addition to the flame retardant.
Substantially anhydrous sodium antimonate treated at an elevated temperature of at least ℃ is preferred. Further, zirconium oxide, zinc sulfide, barium sulfate, or the like may be used in combination with the antimony compound. The amount of the antimony compound to be added is preferably a ratio of one antimony atom per 2 to 5 bromine atoms in the composition.

In the flame-retardant resin composition of the present invention, 0.01 to 2 parts by weight based on 100 parts by weight of the total of the thermotropic liquid crystal polyester (A) and the thermoplastic resin (B).
It is preferable to add 0 parts by weight of the epoxy compound from the viewpoint of heat resistance during the stagnation of the molding. In this case, it is more preferable to add the epoxy compound so that 0.001 to 0.01 g equivalent of the epoxy group is contained.

Examples of the epoxy compound include glycidyl ethers such as bisphenol A diglycidyl, orthophenylphenol glycidyl ether, bisphenol A type epoxy compounds represented by the following structural formula (1), hexahydrophthalic acid diglycidyl ester, and tetrahydrophthalic acid diglycidyl ester. Glycidyl esters such as glycidyl ester, glycidyl ether esters of the following structural formula (2), ethylene / glycidyl methacrylate copolymer containing 1 to 30% by weight of glycidyl methacrylate, and ethylene / glycidyl methacrylate / vinyl acetate copolymer Epoxy group-containing copolymers such as polymers, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimeth Epoxysilanes such as xysilane are exemplified, and among these, epoxysilanes are most preferable.

[0080]

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(N is an integer of 0 to 20)

[0082]

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(Ar represents 1,4-phenylene, 1,3-phenylene, 2,6-naphthylene, etc., and n represents 0 to 2
It is an integer of 0. In addition, the flame-retardant resin composition of the present invention contains an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites and substituted products thereof) to the extent that the object of the present invention is not impaired. ), UV absorbers (such as resorcinol, salicylate, benzotriazole, benzophenone, etc.),
Lubricants and release agents (such as montanic acid and its salts, esters thereof, half esters thereof, stearyl alcohol, stearamide and polyethylene wax), dyes (such as nigrosine) and pigments (such as cadmium sulfide, phthalocyanine, carbon black)
Ordinary additives such as a coloring agent, a plasticizer, and an antistatic agent, and other thermoplastic resins can be added to impart predetermined characteristics.

The flame-retardant resin composition of the present invention is preferably produced by melt-kneading, and a known method can be used for melt-kneading. For example, a Banbury mixer,
The composition can be melt-kneaded at a temperature of 200 to 400 ° C. using a rubber roll machine, a kneader, a single-screw or twin-screw extruder, or the like to obtain a composition.

[0085]

The present invention will be described in more detail with reference to the following examples.

Reference Example 1 881 parts by weight of p-hydroxybenzoic acid, 158 parts by weight of 4,4'-dihydroxybiphenyl, 141 terephthalic acid
Parts by weight and 245 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g were charged into a reaction vessel equipped with a stirring blade and a distillation tube, and subjected to deacetic acid polycondensation under the following conditions.

First, 100 to 250 under a nitrogen gas atmosphere
5 hours at 250 ° C. and 1.5 hours at 250-300 ° C., then reduced to 0.5 mmHg at 300 ° C. for 1 hour, and further reacted for 2.25 hours to complete the polycondensation. Amount of acetic acid was distilled off to obtain resin (a) having the following theoretical structural formula.

[0088]

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K / l / m / n = 75/10/15/25 Further, this polyester was placed on a sample stage of a polarizing microscope, and
As a result of raising the temperature and confirming the optical anisotropy, the liquid crystal onset temperature was 264 ° C., indicating good optical anisotropy. The melting point (Tm) was 294 ° C. The logarithmic viscosity of this polyester (measured in pentafluorophenol at a concentration of 0.1 g / dl at 60 ° C.) is 1.98 dl / g, and the melt viscosity at 304 ° C. and a shear rate of 1000 / sec is 7.
It was 80 poise. 1/8 "thickness x 1 of this polymer alone
The deflection temperature under load (18.56 kgf / cm ² ) of a test specimen having a thickness of 1/8 ″ of a width of 2 ″ × 5 ″ was measured to be 213 ° C.
Met.

Reference Example 2 994 parts by weight of p-hydroxybenzoic acid, 222 parts by weight of 4,4'-dihydroxybiphenyl, 147 parts by weight of 2,6-diacetoxynaphthalene, 1078 parts by weight of acetic anhydride and 299 parts by weight of terephthalic acid were stirred. Charged into a reaction vessel equipped with blades and a distilling tube,
After reacting at 0 ° C. for 5 hours and at 250 to 330 ° C. for 2.5 hours, the pressure was reduced to 1.0 mmHg at 330 ° C. for 1.5 hours, and further reacted for 0.75 hours to complete the polycondensation. An almost theoretical amount of acetic acid was distilled off to obtain a resin (b) having the following structural formula.

[0091]

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K / l / m / n = 80 / 13.3 / 6.7 / 20 Further, the polyester was placed on a sample stage of a polarizing microscope, and
When the temperature was raised and the optical anisotropy was confirmed, the liquid crystal onset temperature was 296 ° C., indicating good optical anisotropy. The logarithmic viscosity of the polyester (measured under the same conditions as in Reference Example 1) was 5.8. 336 ° C, shear rate 10
The melt viscosity at 00 / sec was 920 poise. 1/8 "thickness x 1/2" width x 5 "length of this polymer alone 1/8"
Deflection temperature under load of thick test piece (18.56 kgf / cm ² )
Was 239 ° C.

Reference Example 3 757 parts by weight of p-acetoxybenzoic acid and 538 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g were charged into a reaction vessel equipped with a stirring blade and a distilling tube. Deacetic acid polycondensation was performed under the conditions.

First, 250 to 280 in a nitrogen gas atmosphere.
After reacting at 3 ° C. for 3 hours, the pressure was reduced to 1 mmHg, and the reaction was further continued for 5 hours to complete the polycondensation, thereby obtaining a resin (c) having the following theoretical structural formula.

[0095]

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K / l / m = 60/40/40 The polyester was placed on a sample stage of a polarizing microscope and heated to confirm the optical anisotropy.
74 ° C. The logarithmic viscosity of the polyester (measured under the same conditions as in Reference Example 1) was 0.65, and the melt viscosity at 214 ° C. and a shear rate of 1000 / sec was 3,200 poise. 1/8 "thickness x 1/2" width x of this polymer alone
Deflection temperature under load of a 5 "long test piece (18.56 kgf / cm
² ) was 64 ° C.

Example 1 Thermotropic liquid crystal polyester (a) 8 of Reference Example 1
5 parts by weight and a logarithmic viscosity of 0.65 (0.5 g / dl in orthochlorophenol, 15 parts by weight of polyethylene terephthalate measured at 25 ° C., 80 parts by weight of dibrominated styrene having a weight average molecular weight of 6.7 × 10 ⁴ ) % By weight, 1 monobrominated styrene
5% by weight of polybrominated styrene containing 5% by weight of tribrominated styrene (59% bromine content , brominated styrene monomer
After mixing the prepared ones) 8.0 parts by weight of sodium antimonate 4 parts by weight of a ribbon blender from using vented extruder of 40mmφ set at 300 ° C., melt kneading - and pelletized. Next, the obtained pellets are supplied to a Sumitomo Nestal injection molding machine / Promat 40/25 (manufactured by Sumitomo Heavy Industries, Ltd.), and the cylinder temperature is 300 ° C., the mold temperature is 90 ° C., and the thickness is １ ／ ″. A test piece of × 1/2 ”width × 5” length, ASTM No. 1 dumbbell, and a combustion test piece (1/32 ”thickness ××” width × 5 ”length) were formed.

These test pieces were subjected to an appearance test and a vertical combustion test in accordance with UL94 standard. The deflection temperature under load was measured by using a deflection temperature measuring device manufactured by Toyo Seiki Co., Ltd. to measure the deflection temperature under load (18.56 kgf / cm ² ) of a test piece having a length of ８ ″ thickness × １ ／ ″ width × 5 ″ length. Further, a tensile test was performed according to ASTM D638 standard.

As a result, in the combustion test, 1/32 "V-0
And the deflection temperature under load was 199 ° C. Further, the tensile strength was 1370 kgf / cm ² , which proved that the mechanical properties were excellent and the molded article had a good appearance. Furthermore, after having been retained in the molding machine for 20 minutes, molding was performed and the retention stability was examined. As a result, the tensile strength was 1310 kg.
It was found that there was almost no decrease in physical properties of f / cm ² (retention rate: 96%). Further, as a result of visually examining the color tone of the molded article after staying, the color tone of the molded article hardly changed as compared with the case where there was no stay.

Example 2 When performing melt kneading and pelletizing, an epoxy compound (γ-
A test piece was molded in the same manner as in Example 1 except that 1.5 parts by weight of (glycidoxypropyl) trimethoxysilane was added.
The same items as in Example 1 were evaluated.

As a result, in the combustion test, 1/32 "V-0
And the deflection temperature under load was 199 ° C. Also, the tensile strength was 1380 kgf / cm ² , and it was found that the molded article had excellent mechanical properties and a good appearance of the molded product. Further, the retention stability was examined in the same manner as in Example 1. As a result, the tensile strength was 1370 kgf / cm ² (retention rate: 99%), and there was almost no decrease in the physical properties.

90 parts by weight of the thermotropic liquid crystal polyester (A) [(a), (b)] of Examples 3 to 9 and Reference Examples 1 and 2 and 10 parts by weight of the thermoplastic resin (B) shown in Table 1 (total) (100 parts by weight), based on polybrominated styrene having a weight average molecular weight shown in Table 1 (bromine content: 59% , manufactured from brominated styrene monomer)
Table 1 was intended) (D) and antimony compound (E)
After mixing at the ratio shown in
The mixture was melt-kneaded and pelletized with a 40 mmφ vented extruder set at 0 to 330 ° C. This composition pellet is supplied to a Sumitomo Nestal injection molding machine / Promat 40/25 (manufactured by Sumitomo Heavy Industries, Ltd.), and the cylinder temperature is 260-3.
A test piece similar to that of Example 1 was molded under the conditions of 30 ° C. and a mold temperature of 40 to 90 ° C., and the appearance of the test piece was observed. Then, a vertical combustion test, a deflection temperature under load, and a tensile strength according to UL94 standard were measured, and the molding retention stability was examined by the method of Example 1. Table 1 also shows these results.

[0103]

[Table 1]

It was found that all of them were excellent in appearance of molded articles, flame retardancy, and retention stability during molding. Comparative Examples 1 to 6 of thermotropic liquid crystal polyesters (A) [(a) to (c)] of Reference Examples 1 to 3 and a logarithmic viscosity of 0.65 (0.5 g / dl in orthochlorophenol, measured at 25 ° C.) Polyethylene terephthalate (B), a polybrominated styrene containing 80% by weight of dibrominated styrene having a weight average molecular weight of 6.7 × 10 ⁴ , 15% by weight of monobrominated styrene, and 5% by weight of tribrominated styrene (brominated) 59% content , bromine
Styrene monomer those prepared from) (D) or poly <br/> prepared by bromination of styrenic weight average molecular weight 1
0 × 10 ⁴ tribrominated polystyrene (D ′) and the antimony compound (E) were blended in the proportions shown in Table 2, mixed with a ribbon blender, and set at 260 to 330 ° C. 40
The mixture was melt-kneaded and pelletized by an extruder with a vent of mmφ.

The composition pellets were heated at a cylinder temperature of 26.
Example 1 under the conditions of 0 to 330 ° C and a mold temperature of 40 to 90 ° C
A test piece similar to the above was molded, and the appearance of the test piece was observed.
Then, a vertical combustion test according to UL94 standard, a deflection temperature under load, and a tensile strength were measured. Further, the retention stability was evaluated according to the method of Example 1. Table 2 also shows these results.

[0106]

[Table 2]

[0107] than the results in Table 2, compared to Example 1-9, using a three-brominated polystyrene (D') having a weight-average molecular weight 10 × 104 produced by bromination of polystyrene (Comparative Example In Nos. 1 to 3, 6), the retention stability during molding was poor, and brown coloring was observed in the molded product. When the thermotropic liquid crystal polyester (c) other than the present invention was used (Comparative Examples 5 and 6), the flammability was reduced to 1/3.
It was found that V-0 could not be cleared with a 2 "thickness.

Example 10 Except that 45 parts by weight of glass fiber (C) and 1.5 parts by weight of (γ-glycidoxypropyl) trimethoxysilane were newly added as an epoxy compound during melt kneading and pelletizing. A test piece was molded in the same manner as in Example 1, and the same items as in Example 1 were evaluated.

As a result, in the combustion test, 1/32 "V-0
And the deflection temperature under load was 228 ° C. Further, the tensile strength was 14,10 kgf / cm ² , and it was found that the mechanical properties were excellent and the molded article had a good appearance. Further, the retention stability was examined in the same manner as in Example 1. As a result, the tensile strength was 1390 kgf / cm ² (retention rate: 99%), there was almost no decrease in physical properties, and the color tone of the molded product was good without any change.

Examples 11 to 13, Comparative Examples 7 to 9 Thermotropic liquid crystal polyesters (A) [(a) to (c)] of Reference Examples 1 to 3 and thermoplastic resins (B) shown in Table 3 (total 100). Parts by weight) to glass fiber (3
mm length, 10 μm diameter chopped strand) (C), polybrominated containing 80% by weight of dibrominated styrene having a weight average molecular weight of 10 × 10 4, 15% by weight of monobrominated styrene, and 5% by weight of tribrominated styrene Styrene (bromine content 59
% , Prepared from brominated styrene monomer ) (D) or tribrominated polystyrene (D ') having a weight-average molecular weight of 10.times.10@4 produced by bromination of polystyrene and antimony compound (E) as shown in Table 3. At a set temperature of 260 to 330 ° C. as in Examples 1 to 10.
After kneading and pelletizing at a cylinder temperature of 260
To 330 ° C. and the mold temperature of 40 to 90 ° C.
A test piece similar to that of No. 10 was molded, and the appearance of the test piece was observed and UL was observed.
The vertical combustion test, the deflection temperature under load, and the tensile strength according to the 94 standard were measured. Further, the retention stability was evaluated according to the method of Example 1. Table 3 also shows these results.

[0111]

[Table 3]

From the results shown in Table 3, the composition obtained by adding a thermoplastic resin to a thermotropic liquid crystal polyester having a limited structure according to the present invention and having a deflection temperature under load of 150 to 280 ° C. was compared with a polybrominated styrene. (D), the flame retardancy even when the antimony compound composition obtained by blending (E) is containing filler (C), excellent retention stability during molding, in particular prepared by bromination of polystyrene It was found that the retention stability during molding was remarkably improved as compared with the case where tribrominated polystyrene (D ') having a weight average molecular weight of 10.times.10@4 was used.

[0113]

The flame-retardant resin composition of the present invention has flame-retardant properties,
It has excellent mechanical properties and retention stability during molding, and can be used in various applications as an engineering plastic.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 71/10 C08L 71/10 71/12 71/12 77/00 77/00 81/04 81/04 81/06 81/06 87/00 87/00 (56) References JP-A-64-16859 (JP, A) JP-A-64-48852 (JP, A) JP-A-1-118567 (JP, A) JP-A-1-190750 (JP, a) JP flat 3-95255 (JP, a) JP flat 3-179051 (JP, a) JP flat 4-225055 (JP, a) (58 ) investigated the field (Int.Cl. ⁶ , DB name) C08L 67/00-67/08 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] (A) The following (I), (II), (IV) or (I)
, (II), (III), and (IV), 1 to 99% by weight of a thermotropic liquid crystal polyester having a deflection temperature under load of 150 to 280 ° C; At least one thermoplastic resin selected from lenoxide, semi-aromatic polyester, polyarylene sulfide, polysulfone, polyethersulfone, amorphous polyarylate, and polyetheretherketone
With respect to 100 parts by weight of the resin composition consisting of １1% by weight, (Where R ₁ in the formula is And R ₂ 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 (III)
Total a structural unit (IV) is substantially equimolar. (C) a filler of 0 to 200 parts by weight, and (D) a weight average molecular weight of 1 × 10 ³ to ³ having the following structural unit as a main component produced from a brominated styrene monomer.
A flame-retardant resin composition comprising 0.5 to 60 parts by weight of 0 × 10 ⁴ polybrominated styrene and 0 to 30 parts by weight of (E) an antimony compound. Embedded image 2. The flame-retardant resin composition according to claim 1, wherein the thermotropic liquid crystal polyester (A) contains an ethylenedioxy unit as an essential component.