JPH03179051A - Flame-retardant composition - Google Patents

Abstract

PURPOSE:To improve the heat resistance, flame retardance, appearance after molding, and electrical properties by compounding a specific resin compsn. with an org. bromine compd., an antimony compd., an epoxy compd., and a filler. CONSTITUTION:A resin compsn. is obtd. by compounding 1-10wt.% thermotropic liq. crystal polyester having a deflection temp. under load of 150-280 deg.C and comprising at least one unit selected from the group consisting of units of formulas I, II, and III, and IV or V, [wherein X is formula VI to X; carbonyl groups in formula V are attached to p- or m-position to each other and 60% or higher are at p-position; and the molar amt. of the unit of formula V is substantially equal to that of the sum of the units of formulas II, III, and IV] with 99-90wt.% thermoplastic resin selected from the group consisting of a polyamide, polyoxymethylene, polycarbonate, etc. Then, 100 pts.wt. resulting compsn. is compounded with 0.5-50 pts.wt. org. bromine compd., 0-30 pts.wt. antimony compd., 0.01-20 pts.wt. epoxy compd., and 0-200 pts.wt. filler to give the title compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a flame retardant composition having excellent heat resistance, flame retardancy, molded product appearance and electrical properties.

<Conventional technology> In recent years, the demand for higher performance plastics has been increasing, and many polymers with various new performances have been developed and put on the market. Oriental liquid crystal polymers have attracted attention because of their excellent fluidity and mechanical properties. However, the liquid crystal polymers known so far have a low deflection temperature under load and do not necessarily have sufficient heat resistance, and although they have good heat resistance, their melting points are too high and cannot be formed unless the temperature exceeds 400°C. It has been difficult to obtain a polymer with a good balance between heat resistance and moldability.

On the other hand, it is known that many thermoplastic polymers are inferior to liquid crystal polymers in fluidity and mechanical properties during molding, and that their heat resistance is not necessarily sufficient.

Therefore, in order to improve the fluidity and mechanical properties of thermoplastic polymers during molding, it has been proposed to add various liquid crystal polymers to prepare compositions (Japanese Patent Laid-Open No. 56-115
357, JP-A-57-51739, etc.).

In general, liquid crystalline polyester has flame resistance, and when exposed to direct flame, it has a tendency to form a carbonized layer by self-foaming (MaterialsEBimceriB
Magazine (February 1980 issue, ``Foamed Fire Retardant Paint - Two Most Important Defense Methods against Flames'').

However, thermoplastic resins generally have inferior flame retardancy and electrical properties compared to liquid crystal polyester, and thermoplastic resins with bonds in esters (polyethylene terephthalate, polybutylene terephthalate, etc.) do not have sufficient hydrolysis resistance. It has been known.

<Problems to be Solved by the Invention> Therefore, organic bromine compound flame retardants and antimony trioxide are added to the liquid crystal polymer described in Japanese Patent Publication No. 56-18016 and the blend of the liquid crystal polymer and thermoplastic polymer described in Japanese Patent Publication No. 47-47870. As a result of adding flame retardant, the heat resistance may be insufficient, or conversely, the heat resistance may be sufficient but the processing temperature during compounding is too high and the thermoplastic polymer or flame retardant itself decomposes. However, it was found that a practical composition could not be obtained.

In addition, among liquid crystal polyesters, liquid crystal polyesters (polymer described in Japanese Patent Publication No. 18016/1983), which are obtained by copolymerizing polyesters obtained from alkylene glycol and dicarboxylic acid with acyloxy aromatic carboxylic acids, and among thermoplastic resins, polymers with ester bonds are also used. Compositions obtained by blending polyethylene terephthalate (polyethylene terephthalate, polybutylene terephthalate, etc.) have problems such as insufficient hydrolyzability and arc resistance.

An object of the present invention is to obtain a flame-retardant composition that has excellent heat resistance, flame retardancy, molded product appearance, and electrical properties.

Means for Solving the Problems] The present inventors have conducted intensive studies to solve the above problems, and have arrived at the present invention.

That is, the present invention provides: (A) a thermotropic liquid crystalline polyester 1 having a deflection temperature under load of 150 to 280°C, which is composed of one or more structural units selected from the following 13Ia units, ■, ■, and structural unit 0 or (IV); ~10 Qfi amount%, and (6) from polyamide, polyoxymethylene, polycarbonate, polyarylene oxide, semi-aromatic polyester, polyarylene sulfide, polysulfone, polyether sulfone, amorphous polyarylate, polyether ether ketone One or more selected thermoplastic resins 99
~Of! -+0-X with respect to 100 parts by weight of a resin composition consisting of
-0+...(I[) 1+0CH2CH20-(IV) represents one or more groups selected from number H3, and the carbonyl groups of the 4W3D unit (■) are mutually para or meta. There is a relationship between
65 mol% or more of it is at the para position. In addition, the structural unit ■
is substantially equimolar to the structural unit (@4-(1+■)).

tc>Organic bromine compound 0.5 to 50 parts by weight, ([)) antimony compound 0 to 30 parts by weight, ([)] 1ζoxy compound 0. The present invention provides a vehicle combustible composition characterized in that it contains 1 to 20 parts by weight of O and 0 to 200 parts by weight of filler.

Thermotropic liquid crystal polyester in the present invention (^
) The above structural unit ■ is a structural unit of polyester produced from p-hydroxybenzoic acid, and the above structural unit O is a 4
．． The structural unit 0 is a structural unit produced from 4'-dihydroxybiphenyl, and the structural unit 0 is a structural unit produced from one or more dihydroxy compounds selected from hydroquinone, t-butylhydroquinone, phenylhydroquinone, and 2,6-hydroxynaphthalene. , the structural unit (■) represents a structural unit produced from ethylene glycol, and the structural unit (■) represents a structural unit produced from terephthalic acid and/or isophthalic acid.

The thermotropic liquid crystal polyester (A) of the present invention is a copolymer consisting of one or more structural units selected from the above-mentioned 411 structural units (1), (2), (2) and the structural unit @ or (2).

The amount of copolymerization of the structural units ①, @, (ID and ①) is preferably the following from the viewpoint of fluidity.

In other words, when the above structural unit ■ is included, the above structural unit [■-t■+] is 77 of [■+@-t-@l-@) from the viewpoint of heat resistance, flame retardance, and mechanical properties. -95 mol% is preferable, 82-92 mol% is more preferable, and
The M3fi unit O is preferably 23 to 5 mol%, more preferably 18 to 8 mol% of ((1) 101000).

In addition, the molar ratio of the structural unit ■/[O+■] is preferably 75/25 to 9515 from the viewpoint of heat resistance and fluidity,
More preferably 78/22 to 93/7. Further, the structural unit (3) is substantially equimolar to the 411+ structural unit [00/10].

On the other hand, when the above-mentioned structural unit O is not included, from the viewpoint of fluidity, the above-mentioned structural unit is particularly preferable, and the above structural unit o
The molar ratio of /@ is preferably 9/1 to 1/9, more preferably 7.5/2゜5 to 4/6 from the point of heat resistance and fluidity. Furthermore, in this case, the structural unit O is 2 The one produced from .6-dihydro-xynaphthalene is most preferred, and the structural unit (2) is substantially equimolar to the structural unit [@+G[)).

Thermotropic liquid crystal polyester in the present invention (^
), it is essential that the deflection temperature under load is 150 to 280°C, preferably 190 to 280°C.

If the deflection temperature under load is less than 150°C, the effect of improving the sharpness of the image will be insufficient, and if it exceeds 280°C, if a thermoplastic polymer is blended, the thermoplastic polymer may thermally decompose or the resulting resin composition may be molded. A problem arises in that the temperature increases.

Here, the deflection temperature under load is based on AS1'M D648, and a test piece of 1/8" x 1/2" x 5" is measured at 18.
This is a value measured at a stress of 6 kg/-.

The method for producing the thermotropic liquid crystal polyester (8) in the present invention is not particularly limited, and can be produced according to known polyester polycondensation methods.

For example, if the above structural unit 0 is not included, (1) to (4
), and when the structural unit (■) is included, the production method (5) is preferred.

(1) rM by deacetic acid polycondensation reaction from diacylated aromatic dihydroxy compounds such as p-acetoxybenzoic acid, 4,4'-diacetoxybiphenyl, and paraacetoxybenzene and aromatic dicarboxylic acids such as terephthalic acid.
How to build.

(2) Aromatic dihydroxy compounds such as p-hydroxyammonium, q, aromatic acid, 4,4'-dihydroxybiphenyl, and hydroquinone, and aromatic dicarboxylic acids such as terephthalic acid are reacted with acetic acid to form phenolic hydroxyl groups. After acylation, it is produced by deacetic acid polycondensation reaction.

(3) Phenylnisder of p-hydroxybenzoic acid, 4
．． A method for producing by dephenol polycondensation reaction from an aromatic dihydroxy compound such as 4'-dihydroxybiphenyl or hydroquinone and a diphenyl ester of an aromatic dicarboxylic acid such as terephthalic acid.

(4) After reacting aromatic dicarboxylic acids such as p-hydroxybenzoic acid and terephthalic acid with a desired amount of diphenyl carbonate to form diphenyl esters,
4. Add aromatic dihydroxy compounds such as 4'-dihydroxybiphenyl and hydroquinone to remove phenol M
A method for producing by X1a synthesis reaction.

(5) Polyester or oligomer consisting of ethylene glycol and terephthalic acid and/or isophthalic acid, or bis(β) of terephthalic acid and/or isophthalic acid.
-Hydroxyethyl) ester according to method (1) or (2).

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

The thermotropic liquid crystal polyester (^) of the present invention is
It is also possible to measure the logarithmic viscosity in pentafluorophenol, in which case 0.1 g/d
0.5 dIt/value measured at 60°C at a concentration of 1
g or more, particularly preferably 1.0 to 3.0 dl/g when the structural unit O is included, and preferably 2.0 to 10, Od1/r when the structural unit O is not included.

Further, the melt viscosity of the aromatic polyester of the present invention is 10 to
20,000 boiz is preferred, especially 20 to 10. O
OO bois is more preferred.

Note that this melt viscosity is a value measured using a Koka type flow tester under conditions of (liquid crystal start temperature + 40° C.) and a slip rate of 1.000 (1/sec).

In addition, when polycondensing the aromatic bolier stellate of the present invention, in addition to the components constituting the above structural units (1), (2), 0, (2), and (2), 4.4'-diphenyldicarboxylic acid, 3.3'
-diphenyldicarboxylic acid, 3.4'-diphenyldicarboxylic acid, 2゜2'-diphenyldicarboxylic acid, 1.2
-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 1,2-bis(2-chlorophenoxy)ethane-4,
Aromatic dicarboxylic acids such as 4-dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, and 2,6-naphthalene dicarboxylic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, resorcinol, talolhydroquinone,
Methylhydroquinone, 2.7-dihydroxynaphthalene, aromatic dihydroxy compounds such as 4.4-dihydroxydiphenyl ether, m-oxybenzoic acid, 2.6-
Aromatic oxycarboxylic acids such as oxynaphthoic acid, p-aminophenol, p-aminoamine, aromatic acid, etc. can be further copolymerized within 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,
One or more thermoplastic resins (B) selected from polysulfone, polyethersulfone, -II polyarylate, and polyneedleetherketone may be blended, and in this case, the deflection temperature under load is less than 190°C. is preferred.

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

Polyamides include nylon 6, nylon 46, nylon 66, nylon 610, nylon 11, and nylon 1.
2 and copolymers thereof. Examples of polyoxymethylene include polyoxymethylene homopolymers and copolymers in which the main chain is mostly composed of oxymethylene chains. Polycarbonates include bis(4-hydroxyphenyl), bis(3,5-dialkyl-4-human, roxyphenyl) or bis(3,5-
Polycarbonates based on hydrocarbon derivatives containing dihalo-4-hydroxyphenyl) substitution are preferred; 2,2-bis(4-hydroxyphenyl)propane (
Particularly preferred polyarylene oxides are polycarbonates based on bisphenol A), such as poly(2,6-dimethyl-1,4-phenylene) ether,
2.6-dimethylphenol/2,3.6-dimethylphenol copolymer, 2゜6-dimethylphenol/2
, 3.6-1 recycled tylphenol copolymer, and the like.

Styrenic resins such as polystyrene and impact-resistant polystyrene can be added to the polyarylene oxide.

Examples of the semi-aromatic polyester include polyalkylene terephthalates such as polyethylene terephthalate and polybutylene terephthalate.

Examples of polyarylene sulfide include polyparaphenylene sulfide.

Structural formula for polysulfone Examples include those expressed as:

Structural formula for polyether sulfone Examples include those expressed as:

As amorphous polyarylate, Structural formula Examples include those expressed as:

polynyderetherketone and Then, structure formula, Examples include those expressed as:

Among the above thermoplastic resins (B) used in the present invention, polyamides, polycarbonates, semi-aromatic polyesters, amorphous polyarylates, and polyarylene sulfides can be particularly preferably used.

In the present invention, the blending amount of the thermotropic liquid crystal polyester (8) is 1 to 100% by weight, preferably 5 to 100%.
The amount of plastic resin (B) added to the dwarf percentage is 99 to 0]
1! The amount % J should preferably be between 95 and 0% by weight. Thermotropic liquid crystal polyester (^) 1% by weight
If it is less than that, the clarity, fluidity and mechanical properties will be insufficient.

The organic bromine compound used as component (C) in the present invention has a bromine atom in its molecule, and means a known organic bromine compound that is usually used as a flame retardant, particularly one with a bromine content of 20% by weight. Preferably the above
Specifically, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl,
Hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)
Ethane, ethylene bis-(tetrabromophthalimide)
, low molecular weight organic bromine compounds such as detrabromobisphenol A, brominated polycarbonates (e.g., polycarbonate oligomers produced from brominated bisphenol A, or copolymers thereof with bisphenol A), brominated epoxy compounds (e.g., brominated bisphenol A), Jepoxy compounds produced by the reaction of bisphenol A and epichlorohydrin, and monoepoxy compounds produced by the reaction of brominated phenols and epichlorohydrin?
! ! 3), poly(brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A,
Examples include halogenated polymers and oligomers, such as condensates of cyanuric chloride and brominated phenols, brominated polystyrene, crosslinked brominated polystyrene, crosslinked brominated polyα-methylstyrene, and mixtures thereof. Bromophthalimide), brominated epoxy oligomers or polymers, brominated polystyrene, crosslinked brominated polystyrene, brominated polyphenylene ethers and brominated polycarbonates are preferred, especially ethylene bis(tetrabromophthalimide), brominated polystyrene, crosslinked brominated polystyrene, bromine Polyphenylene ether and brominated polycarbonate are preferably used.

Among the above-mentioned preferred organic bromine compounds, the brominated epoxy polymer represented by the following general formula (i) is preferred.

The degree of polymerization n in the above general formula (i) is preferably 15 or more,
Further, jF is preferably 50 to 80.

Moreover, as the brominated polystyrene, those represented by the following formula (i i1) are preferable.

r3 Furthermore, as the crosslinked brominated polystyrene, polystyrene obtained by brominating porous polystyrene crosslinked with divinylbenzene is preferable.

As the brominated polycarbonate, the following general formula (iii
) is preferred.

(Rj and R2 represent a substituted or unsubstituted aryl group, most preferably a pt-butylphenyl group).

The degree of polymerization n in the above general formula (iii) is preferably 4 or more, and more preferably 8 or more, particularly 8 to 25.

The amount of these organic bromine compounds (C) added is 0.5 to 50 parts by weight, preferably 1 to 30 parts by weight per 100 parts by weight of the liquid crystal polyester.

If the amount added is less than 0.5 parts by weight, flame retardancy will not be sufficient,
If it exceeds 50 parts by weight, the physical properties of the composition will deteriorate, which is not preferable.

In the present invention, an antimony compound can be used as component (D). There are no particular restrictions on the antimony compound as long as it is normally used as a flame retardant aid for polyester, but sodium antimonate is preferred, and zirconium oxide, zinc sulfide, barium sulfate, etc. may be used in combination with the antimony compound. The sodium antimonate is preferably substantially anhydrous sodium antimonate that has been aged at a high temperature of 550 DEG C. or higher, and preferably has an average particle size of 1 to 30.

In the present invention, the amount of the antimony compound added is 0 to 30 parts by weight per 100 parts by weight of the liquid crystal polyester. The amount of addition is preferably the minimum amount necessary to obtain flame retardancy.For example, liquid crystal polyester and polycarbonate, polyarylene oxide, polyarylene sulfide, polysulfone, polyneedle sulfone, amorphous polyarylate, In the case of a thermoplastic resin composition such as polyether ether getone or a composition containing no thermoplastic resin, flame retardation can be achieved with only a bromine compound.

The epoxy compound used as component (E) in the present invention is not necessarily limited to glycidyl ethers synthesized from phenols and epichlorohydrin, such as bisphenol octadiglycidyl ether, ortho-phenylphenol glycidyl ether, and hexahydro- Glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, glycidyl methacrylate, p
- Glycidyl esters and ethers made of hydroxycarboxylic acids and epichlorohydrin such as glycidyl esters and ethers of hydroxybenzoic acid; epoxidized imide compounds such as N-glycidyl phthalimide; Epoxy group-containing copolymers consisting of a saturated monomer and other unsaturated monomers such as ethylene, or epoxysilanes commonly used as silane coupling agents, such as γ-glycidoxypropyltrimethoxysilane, etc. Can be mentioned.

Among the above-mentioned epoxy compounds, preferred specific examples of glycidyl ethers include ortho-phenylphenol glycidyl ether and bisphenol A type epoxy compounds represented by the following formula (1).

The value of the degree of polymerization n of the compound of formula H30 is 0 or an integer of 1 to 20, and is 0 or 1 to . An integer of 10 is preferred, and
It may be a mixture of compounds having various degrees of polymerization.

Preferred specific examples of glycidyl esters include hexahydrophthalic acid diglycidyl ester and tetrahydrophthalic acid glycidyl ester.

Preferred specific examples of chrycidyl ethers and esters include the following epoxy compounds of the formula (4).

O (However, in the formula, Ar represents an aromatic group or alicyclic group having 6 to 20 carbon atoms, and n represents O or an integer of 1 to 20.) Specific examples of Ar include 1,4-phenylene, 1.3-
Phenylene, 1,2-phenylene, 2-methyl-1,4
-phenylene, 4.4'-biphenylene, 3.3'-biphenylene, 2.2'-biphenylene, 3,4'-biphenylene, 1.4-naphthylene, 1.5-naphthylene,
2.6-naphthylene, 2゜7-naphthylene, 1.4-cyclohexylene, 1゜3-cyclohexylene, 1.2-
Cyclohexylene, 4,4'-bicyclohexylene, 2
．． Preferred examples include 6-zocahydronaphthylene,
Among them, 1,4-phenylene, 1,3-phenylene and 2,6-naphthylene are particularly preferred.

It is particularly preferable that the average degree of polymerization (n) is in the range of 0 to 5, and that the weight average molecule Ji (Mw>) and the number average molecule Ji (M
The ratio Mw/Mn of n) is in the range of 1.0 to 3°0. The method for producing the epoxy compound represented by the formula (2) is not particularly limited, but for example, hydroxy, dicarboxylic acid, and epihalohydrin are mixed in the presence of a catalyst such as quaternary ammonium, tertiary amine, or tertiary phosphine. For those with a high degree of polymerization, there is a method of producing halohydrin ester etherification by reacting at ~150°C, and then adding an alkali metal salt to dehydrohalogenate. It can be obtained by reacting an acid with varying ratios in the presence of a catalyst.

Further, as preferred specific examples of the epoxy group-containing copolymer, ethylene/glycidyl methacrylate copolymers and ethylene/glycidyl methacrylate/vinyl acetate copolymers containing 1 to 30% by weight of glycidyl methacrylate are preferred.

Preferred specific examples of epoxysilanes include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxyglopylmethyldimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

Particularly preferred epoxy compounds among the above are the bisphenol A type epoxy compound represented by the above structural formula (1), glycidyl ether nitride and epoxy silanes shown by the above structural formula (2).

The epoxy equivalent of the epoxy compound (E) in the present invention is preferably 100 to 3,000. The epoxy equivalent herein refers to the number of grams of the compound containing an equivalent of 1 epoxy group.

In the present invention, the amount of the organic epoxy compound used as component (E) is 0.01 to 20 parts by weight based on 100 parts by weight of the mature plastic fat composition composed of thermotropic liquid crystal polyester and thermoplastic resin. , epoxy groups are 0.001 to 100 g of a mature plastic resin composition consisting of a thermotropic liquid crystal polyester and a thermoplastic resin.
It is preferable to add the thermoplastic resin composition in an amount of 0.01 st equivalent, more preferably in an amount of 0.002 to 0.008 g equivalent.
When the amount is less than 0.01 part by weight, the effect of improving mechanical properties is small, while when it exceeds 20 parts by weight, there is a drawback that flame retardancy is impaired.

Examples of the filler component (F) that can be used in the present invention include glass fibers, carbon fibers, aromatic polyamide fibers, potassium titanate strands, gypsum fibers, brass fibers, stainless fibers, steel fibers, ceramic fibers, Examples include fibrous, granular, granular, or plate-like =n fillers such as boron whisker fibers, mica, talc, silica, calcium blown acid, glass beads, glass flakes, glass microballoons, clay, wollastenite, and titanium oxide.

Among the above fillers, glass fiber is preferably used. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing resins, and can be selected from, for example, long fiber type, short fiber type chopped strand, milled fiber, etc. Additionally, the glass fibers may be coated or bundled with a thermoplastic resin such as ethylene/vinyl acetate copolymer, a maturing resin such as an epoxy resin, a coupling agent such as a silane type, a titanate type, etc. It may be treated with a surface treatment agent.

When adding a filler, the amount is as follows: Four-fat composition 1002 consisting of thermotropic liquid crystal polyester and thermoplastic resin
T! It is 200 parts by weight or less, more preferably 100 parts by weight or less.

The composition of the present invention may contain antioxidants, heat stabilizers (e.g. hindered phenol, hydroquinone, bosphites, substituted products thereof, etc.), ultraviolet absorbers ( (e.g. resorcinol, salicylate, benzotriazole, benzophenone, etc.), lubricants and mold release agents (montanic acid and its salts, its esters, its half esters, stearyl alcohol, stearamide and polyethylene wax, etc.), dyes (e.g. niacin), etc. ) and pigments (e.g. cadmium sulfide, phthalocyanines, carbon black, etc.), conventional additives such as colorants, plasticizers, antistatic agents, and other thermoplastics can be added to impart the desired properties. .

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

<Example> Hereinafter, the present invention will be explained in detail with reference to Examples.

Sanni 1st edition 1 p-hydroxybenzoic acid 881! T! parts by weight, 158 parts by weight of 4.4-dihydroxybiphenyl, 907 parts by weight of acidic acid, 141 parts by weight of prephthalic acid, and an intrinsic viscosity of about 0.
．． 6 dl/g polyethylene terephthalate2
45 parts by weight was charged into a reaction vessel equipped with a stirring blade and distillation tube, and acetic acid depolycondensation was carried out in the following step r1-.

First, under a nitrogen gas atmosphere at 100 to 250°C for 5 hours,
After reacting at 250-300℃ for 1.5 hours, 300℃
, the pressure was reduced to 0.5 x 11 (] in 1 hour, and then 2.25
When the reaction was carried out for a period of time to complete the polycondensation, almost a theoretical amount of acetic acid was distilled out, resulting in a resin (a) having the following theoretical formation formula.
I got it.

k / 1 / m / n = 75 / 10 /
15/25 In addition, this polyester was placed on a sample stage of a polarized light microscope chain, and the temperature was raised to confirm the optical field Jf properties.As a result, the liquid crystal start temperature was 264 °C, indicating good optical field Jf properties. Indicated. Logarithmic viscosity of this polyester (0,1
in pentafluorophenol at a concentration of g/d1 at 60°C.
) is 1.96dj! /"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-diacedoxynaphthalene, 1078 parts by weight of acetic anhydride, and 299 parts by weight of terephthalic acid. , charged in a reaction vessel equipped with a distillation tube, and heated under nitrogen gas atmosphere for 100~
After reacting at 250°C for 5 hours and at 250-330°C for 2.5 hours, l, Q rma at 330°C for 1.5 hours.
The pressure was reduced to IIg, and the reaction was further continued for 1.5 hours.
When the condensation was completed, a nearly stoichiometric amount of acetic acid was distilled out.
A resin (b) having the following theoretical compression formula was obtained.

ni/j! /m/n=80/13.3/6.7/20 Also, as a result of confirming the optical anisotropy by placing this polyester on the sample stage of a polarizing microscope FR mirror and increasing the temperature, the liquid crystal starting temperature was 300° C., indicating good optical anisotropy. The logarithmic viscosity of this polyester (measured under the same conditions as Reference Example 1) is 6.2 dJ! /g.

Reference example 3 P-acetoxybenzoic acid 1,351 parts by weight, 4゜4゛-
451 parts by weight of diacetoxybiphenyl, 162 parts by weight of hydroquinone diacetate and 31 parts by weight of terephthalic acid.
11 parts by weight of Tf and 104 parts by weight of isophthalic acid were charged into a reaction vessel equipped with a stirring blade and a distillation tube, and the mixture was heated under a nitrogen gas atmosphere for 2 hours.
After reacting at 50-360°C for 3 hours, 1+u+1II
The pressure was reduced to J, and the mixture was further heated for 1 hour to complete the polycondensation.
A resin (C) having the following theoretical lf4 formula was obtained.

k/j! /m/n10=75/ 16.67/8.33
/ 18.75/6.25 This polyester is polarized
When the optical anisotropy was confirmed by placing the sample on a AG sample stage and raising the temperature, the liquid crystal start temperature was 305° C., indicating good optical anisotropy. The logarithmic viscosity of this polyester (measured under the same conditions as Reference Example 1) was 4.1 d 1 /g.

Reference example 4 757 parts by weight of P-acetoxybenzoic acid, intrinsic viscosity is approximately 0
．． 6 d! / t of polyethylene terephthalate 5
38 parts by weight was charged into a reaction vessel equipped with a stirring blade and a distillation tube, and acetic acid depolymerization was carried out under the following conditions.

First, after reacting at 250 to 280°C for 3 hours in a nitrogen gas atmosphere, the pressure was reduced to 1 ml IO, and further heated for 5 hours to complete polycondensation.
d) was obtained.

k/1/m=60/40/40 When this polyester was placed on the sample stage of a polarizing microscope and the temperature was raised to confirm the optical anisotropy, the liquid crystal start temperature was 1.
The temperature was 74°C. The logarithmic viscosity (measured in the same manner as in Reference Example 1) of this polyester was 0.65.

To Example 1-14, Comparative Examples 1 to 7 Thermotropic liquid crystal polyester (A
) Ha) to (d)] and the thermoplastic resin (B
) Organobromine compound (C>, antimony compound (D) ↓, and epoxy compound (E) [:(() to (to)]) for ((^)+100 parts by weight of (B)) in Table 1. Mix at the ratio shown in 260~3 using a 30fiφ twin screw extruder.
The mixture was melt-kneaded at 50°C and pelletized.

This polymer was processed using Sumitomo Nestal injection molding machine Promat 40.
/25 (Sumitomo Heavy Industries ■I! Test piece of 1/8 #xi/2" x 5", combustion test under the conditions of cylinder temperature 260-3.50℃ and mold temperature 40-90℃ A piece (1/32" x 1/2" x 5") was molded.

These test pieces were subjected to outside inspection and vertical combustion tests in accordance with UL94 standards. Then, the load deflection temperature was determined by measuring the load deflection temperature (18,6 kt/-) of a 1/8" x 1/2" x 5" test piece using a load deflection temperature measuring device manufactured by Toyo Seiki. -A
Arc resistance was measured according to S 'I' M D /l 95. The results are shown in Table 1.

As is clear from the results in Table 1, the thermotropic liquid crystalline polyester of the present invention has a deflection temperature under load of 150 to 280°C, or the thermoplastic resin is added to the thermotropic liquid crystalline polyester. The composition obtained by blending an organic bromine compound, an antimony compound, and an epoxy compound with the polymer obtained by adding the organic bromine compound has excellent elegance (particularly for thin-walled molded products), sharpness, and electrical properties. It can be seen that it has the appearance of a molded product.

Examples 15 to 1B, Comparative Examples 8 to 10 Thermotropic liquid crystal polyesters of Reference Examples 1 to 4 (^
)Ha) to (d)), thermoplastic resin (B), brominated polystyrene (Nissan Ferro ■ ``Pyrocheck'')
68PB), antimony compound, Eboji Jt'i!
r'f (=) [(a), (f)], glass fiber (31
11 m long, 10-diameter chopped strands) were melt-mixed and pelletized at a set temperature of 260 to 300°C in the same manner as Examples 1 to I4 and Comparative Examples 1 to 7 in the proportions shown in Table 2, followed by cylinder temperature of 260 to 300'. C1 mold temperature 40~9
Example 1~ under 0°C conditions! 4. Test pieces similar to those in Comparative Examples 1 to 7 were molded, and the outside of the test pieces was subjected to It11 observation, and the vertical combustion test, deflection temperature under load, and tensile strength were measured in accordance with the UL94 standard. These results are also shown in Table 2.

From the results in Table 2, it can be seen that the thermotropic liquid crystal polyester of the present invention having a deflection temperature under load of 150 to 280°C and the composition obtained by adding a thermoplastic resin to this thermotropic liquid crystal polyester are Therefore, the composition obtained by blending an organic bromine compound, an antimony compound, and an epoxy compound has excellent flame retardancy, heat resistance, and electrical properties as well as excellent molded product appearance even when it contains a filler.

<Effects of the Invention> From the resin composition of the present invention, resin molded articles having excellent flame retardancy, electrical properties, molded article appearance, and heat resistance can be obtained.

Claims (1)

[Claims] (A) Consisting of one or more structural units selected from the following structural units (I), (II), (V) and structural units (III) or (IV), the deflection temperature under load is 150. 1 to 100% by weight of thermotropic liquid crystal polyester at ~280°C; (B) polyamide, polyoxymethylene, polycarbonate, polyarylene oxide, semi-aromatic polyester, polyarylene sulfide, polysulfone, polyether sulfone, amorphous one or more thermoplastic resins selected from polyarylates and polyetheretherketones99
▲ There are mathematical formulas, chemical formulas, tables, etc. ▼・・・(I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼・・・(II) ▲ There are mathematical formulas, chemical formulas, tables, etc.▼...(III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(V) (However, X in the formula represents one or more groups selected from ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and the carbonyl groups of the structural unit (V) are mutually para or There is a meta relationship,
65 mol% or more of it is at the para position. Also, the structural unit (
V) is substantially equimolar to the structural unit [(II)+(III)+(IV)]. ) (C) Organic bromine compound 0.5-50
parts by weight, (D) 0 to 30 parts by weight of an antimony compound, (E) 0.01 to 20 parts by weight of an epoxy compound, and (F) 0 to 200 parts by weight of a filler. sexual composition.