JP2000160030A - Flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a novel flame retardant resin composition without any problem on inclusion of halogen elements, which are excellent in flame retardance, mechanical properties, molding processability and the like and, in addition, difficult to cause drips. SOLUTION: This flame retardant resin compositions comprises (A) 100 pts.wt. at least one thermoplastic resin selected from a polycarbonate based resin, a polyphenylene ether based resin, a polyester based resin and a polystyrene based resin, (B) 0.01-50 pts.wt. thermotropic liquid crystal polyester, and (C) 1-30 pts.wt. at least one halogen element-free organic phosphorous compound selected from a phosphine compound, a phosphine oxide compound, a phosphate ester compound, and a condensation phosphate ester compound all of which do not contain any halogen element, and the heat deformation temperature of the thermotropic liquid crystal polyester (B) is higher than that of the thermoplastic resin by 10-100 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel flame-retardant resin composition.

[0002]

2. Description of the Related Art Thermoplastic resins are used in various fields such as OA equipment and home appliances because of their excellent moldability, mechanical properties, appearance, and the like. Problems require flame retardancy.

In order to make a thermoplastic resin flame-retardant, a halogen-containing organic compound such as tetrabromobisphenol A or decabromodiphenyl oxide is generally blended as a flame retardant. However, the compounding of the halogen-containing organic compound reduces the thermal stability of the thermoplastic resin that is the matrix, the gas generated by the decomposition of the halogen-containing organic compound at the time of molding corrodes the mold, and at the time of molding or burning. This causes a problem that toxic halogen compounds having a low molecular weight are produced as by-products.

Further, an organic phosphorus compound containing no halogen element has been proposed as a flame retardant for a thermoplastic resin. For example, a composition in which triphenyl phosphate or a condensable phosphoric acid ester and a tetrafluoroethylene polymer (PTFE) are mixed with a resin mixture composed of an aromatic polycarbonate and a rubber-reinforced styrene resin (EP Patent No. 17)
No. 4493, Netherlands Patent No. 8802346), a composition in which a crystalline powder of an aromatic diphosphate compound is blended with a thermoplastic resin (JP-A-5-1079, US Pat. No. 5,122,556), and the like. An organophosphorus compound containing no halogen can impart a certain degree of flame retardancy to a thermoplastic resin, but has the disadvantage of adversely affecting the mechanical properties and moldability of the resin. Further, since an organic phosphorus compound containing no halogen has a plasticizing effect on the resin, it is likely to cause drip (dripping of a fire at the time of combustion), and therefore, the incorporation of an anti-drip agent such as PTFE is essential.
In particular, UL-94 flame retardancy test method (Test for Flammabil
ity of Plastic Materials forParts in Devices and A
ppliances UL-94, Fourth Edition)
In order to achieve a flame retardancy of −0 level, it is essential to suppress dripping.

On the other hand, for the flame retardation of a resin composition containing a thermotropic liquid crystal polyester and another thermoplastic resin, bromine-containing organic compounds such as brominated polystyrene (JP-A-3-17951), organic phosphorus Compounds (JP-A-7-331051 and JP-A-9-59524) are compounded. However, the compounding of the bromine-containing organic compound causes a decrease in thermal stability, mold corrosion during molding, generation of a toxic bromine compound, and the like, as described above, and further does not show a sufficient effect on drip prevention. . In addition, when an organic phosphorus compound is blended, dripping is liable to occur, and it is essential to use a drip preventing agent such as PTFE or a fibrous inorganic filler in combination.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the problem of containing a halogen element, to provide flame retardancy,
An object of the present invention is to provide a novel flame-retardant resin composition which is excellent in mechanical properties, moldability, and the like, and hardly causes drip even without adding a drip inhibitor.

[0007]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a three-component mixed system of a thermoplastic resin, a thermotropic liquid crystal polyester, and an organic phosphorus compound containing no halogen is used. Even if the thermal deformation temperature of the thermoplastic resin and the thermotropic liquid crystal polyester has a specific relationship, V-0 is determined by the UL-94 test method.
A flame-retardant resin composition having excellent mechanical strength and molding processability, which does not require the addition of an anti-drip agent in addition to the three components.
The present invention has been completed.

That is, the present invention relates to (A) at least one resin selected from the group consisting of a polycarbonate resin, a polyphenylene ether resin, a polyester resin and a polystyrene resin.
Parts of thermoplastic resin, (B) 0.01 to 50 parts by weight of a thermotropic liquid crystal polyester, and (C) a halogen-free phosphine compound, a phosphine oxide compound, a phosphate compound and a condensed phosphate ester It contains 1 to 30 parts by weight of an organic phosphorus compound not containing at least one halogen element selected from compounds, and the heat distortion temperature of (B) thermotropic liquid crystal polyester is higher than that of (A) the thermoplastic resin. The present invention relates to a flame-retardant resin composition which is higher by 10 to 100 ° C.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant resin composition of the present invention comprises:
It contains (A) a specific thermoplastic resin, (B) a thermotropic liquid crystal polyester, and (C) an organic phosphorus compound containing no halogen element as essential components.

(A) As the thermoplastic resin, at least one selected from a polycarbonate resin, a polyphenylene ether resin, a polyester resin and a polystyrene resin is used.

Known polycarbonate resins can be used, for example, an aromatic dihydroxy compound or an optionally branched thermoplastic aromatic compound obtained by reacting an aromatic dihydroxy compound or a polyhydroxy compound with phosgene or a carbonic acid diester. Group polycarbonate polymers or copolymers.

Examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) methane, and 1,1-bis (4-hydroxyphenyl)
Ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert-butyl-
4-hydroxyphenyl) propane, 2,2-bis (4
-Hydroxy-3,5-dimethylphenyl) propane,
2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4)
-Hydroxyphenyl) propane, 1,1-bis (4-
Hydroxyphenyl) -1-phenylethane, bis (4
Bis (hydroxyaryl) cycloalkanes such as -hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-
Bis (hydroxyaryl) cycloalkanes such as bis (4-hydroxyphenyl) cyclohexane, 4,4 ′
Dihydroxydiaryl ethers such as dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenylether, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxy-
Dihydroxydiaryl sulfides such as 3,3'-dimethyldiphenyl sulfide; 4,4'-dihydroxydiphenyl sulphoxide; 4,4'-dihydroxy-
Dihydroxydiarylsulfoxides such as 3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-
Examples thereof include dihydroxydiarylsulfones such as 3,3′-dimethyldiphenylsulfone, hydroquinone, resorcinol, and 4,4′-dihydroxyphenyl. One kind of aromatic dihydroxy compound can be used alone, or two or more kinds can be used in combination. Of these, 2,
2-Bis (4-hydroxyphenyl) propane is particularly preferred.

As the polyhydroxy compound, for example,
Phloroglucin, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -3-heptene, 4,6-
Dimethyl-2,4,6-tri (4-hydroxyphenyl) -2-heptene, 1,3,5-tri (2-hydroxyphenyl) benzol, 1,1,1-tri (4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol,
α, α ', α "-tri (4-hydroxyphenyl)-
Examples thereof include 1,3,5-triisopropylbenzene and 3,3-bis (4-hydroxyaryl) oxindole (ichisan bisphenol). One polyhydroxy compound may be used alone, or two or more polyhydroxy compounds may be used in combination.

When a polycarbonate resin is produced by reacting phosgene, a terminal terminator or a molecular weight regulator may be added to the reaction system. The terminal terminator or the molecular weight regulator may be any compound having a monovalent phenolic hydroxyl group, such as phenol and p-tert-.
Examples thereof include butylphenol, long-chain alkylphenol, aliphatic carboxylic acid chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, and alkyl ether phenol.

Although the molecular weight of the polycarbonate resin is not particularly limited, it is usually a viscosity-average molecular weight calculated from the viscosity of a methylene chloride solution at 25 ° C. of 10,000 to 10,000.
100,000, preferably 15,000 to 50,000.

The polycarbonate resins can be used each alone or two or more of them can be used in combination.

As the polyphenylene ether-based resin,
Known ones can be used, for example, a general formula

[0018]

Embedded image

[In the formula, R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom, a hydrocarbon group or a substituted hydrocarbon group. ]
And homopolymers and copolymers containing the repeating structural unit represented by

More specifically, for example, poly (2,6-
Dimethyl-1,4-phenylene ether), 2,6-
Copolymers of dimethylphenol and 2,3,6-trimethylphenol can be exemplified. Among them, poly (2,6-dimethyl-1,4-phenylene ether) is preferred.

As the polyphenylene ether resin, one type can be used alone, or two or more types can be used in combination.

Known polyester resins can be used, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, ethylene terephthalate and cyclohexane dimethylene terephthalate. And a copolymer of ethylene terephthalate and ethylene isophthalate. The polyester resins can be used each alone or two or more of them can be used in combination.

Known polystyrene resins can be used. For example, in addition to the polystyrene resin itself, a polystyrene resin in which a rubber-like polymer is contained in a matrix of a polystyrene resin in the form of particles, or the like. Copolymer resins of styrene and acrylonitrile and the like can be mentioned.

The polystyrene-based resin containing the rubbery polymer may be an aromatic vinyl monomer as a raw material of the polystyrene resin and optionally another copolymerizable monomer in the presence of the rubbery polymer. The monomer can be produced by polymerizing according to a known method such as bulk polymerization, suspension polymerization, solution polymerization, and emulsion polymerization.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, butylstyrene and the like. Of these, styrene is most preferred, but one or more other aromatic vinyl monomers may be used mainly in combination with styrene. Other copolymerizable monomers include, for example, (meth) acrylate monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, maleimide, N-methylmaleimide, N -Maleimide monomers such as -ethylmaleimide, N-propylmaleimide, N-hexylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide; unsaturated dicarboxylic anhydride monomers such as maleic anhydride; (meth) Acrylonitrile and the like can be mentioned. These monomers can be used alone or in combination of two or more.

The rubbery polymer preferably has a glass transition temperature (Tg) of -30 ° C. or lower in consideration of the impact resistance and the like of the obtained styrene resin. Examples of such rubbery polymers include diene rubbers such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), saturated rubber obtained by hydrogenating the diene rubber, isoprene rubber, and polyacrylic acid. Examples include acrylic rubber such as butyl, ethylene-propylene-diene monomer terpolymer (EPDM), polyurethane rubber, and silicone rubber. One type of rubbery polymer can be used alone, or two or more types can be used in combination.

Specific examples of the polystyrene resin include, for example, impact-resistant polystyrene resin, AS resin (acrylonitrile-styrene resin), ABS resin (acrylonitrile-butadiene-styrene copolymer), and AAS resin (acrylonitrile-acryl rubber- Styrene copolymer), MBS resin (methyl methacrylate-butadiene-styrene resin), AES resin (acrylonitrile-ethylene propylene rubber-styrene copolymer) and MAB
S resin (methyl methacrylate-acrylonitrile-butadiene-styrene resin) and the like can be mentioned.

One type of polystyrene resin can be used alone, or two or more types can be used in combination.

In the present invention, one or more thermoplastic resins (A) selected from a polycarbonate resin, a polyphenylene ether resin, a polyester resin and a polystyrene resin are used. Among them, a resin mixture of one or more selected from a polycarbonate resin, a polyphenylene ether resin and a polyester resin and a polystyrene resin is preferable, and a resin of a polycarbonate resin, a polybutylene terephthalate resin and an ABS resin is preferable. A mixture, a resin mixture of a polyphenylene ether-based resin and an impact-resistant polystyrene-based resin, and the like are particularly preferable. When a polystyrene-based resin and another thermoplastic resin are used in combination, the use ratio is 1/9 by weight.
It may be 9-99 / 1, preferably 5 / 95-95 / 5.

The thermal deformation temperature of the thermoplastic resin (A) is as follows:
Usually, it is preferably about 50 to 200 ° C.

The heat deformation temperature of the resin or polymer in the present specification is defined as a value of 18.6 kgf using a 1/8 inch thick x 1/2 inch wide x 5 inch long molded body according to ASTM D648. heat distortion temperature (° C) measured in cm ²
Say.

As the thermotropic liquid crystal polyester (B), known polyesters can be used, for example, those having an aromatic hydroxycarboxylic acid, a polyalkylenediol and an aromatic dicarboxylic acid as main constitutional units, and aromatic hydroxycarboxylic acids. Main chain type liquid crystal polymers such as those having hydroxynaphthoic acid as a main constituent unit, aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids and dihydroxybiphenyl as main constituent units, polyalkylene diols and aromatics having polyphosphazene as a main chain And those having a side chain of an aromatic carboxylic acid.

Of these, those having p-hydroxybenzoic acid and polyethylene terephthalate as main constitutional units, those having p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid as main constitutional units, dihydroxy compounds and And / or those obtained by polycondensation of a dicarboxy compound. By appropriately selecting the dihydroxy compound and the dicarboxy compound, the flame retardancy (particularly, anti-drip properties) and the mechanical properties can be further improved.

Examples of the dihydroxy compound include, for example, ethylene glycol, hydroquinone, 2,6-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, bisphenol-A and the like. Among these, ethylene glycol, hydroquinone,
4,4′-dihydroxybiphenyl and the like are preferable, and ethylene glycol, hydroquinone and the like are more preferable. Examples of the dicarboxy compound include, for example, terephthalic acid, isophthalic acid, and 2,6-dicarboxynaphthalene. Among these, terephthalic acid and isophthalic acid are preferable, and terephthalic acid is more preferable. The dihydroxy compound and the dicarboxy compound are
One of these can be used alone, or two or more can be used in combination. When terephthalic acid is used as the dicarboxy compound, its amount is usually at least 40% by weight, preferably at least 60% by weight, based on the total amount of the dihydroxy compound and / or the dicarboxy compound. Use 4 terephthalic acid
When the content is 0% by weight or more, a flame-retardant resin composition having more excellent flame retardancy and mechanical strength can be obtained.

The thermal deformation temperature of the thermotropic liquid crystal polyester (B) is usually about 100 to 200 ° C.
Preferably, the temperature is about 115 to 190 ° C.

In the flame-retardant resin composition of the present invention,
(B) The heat deformation temperature of the thermotropic liquid crystal polyester is 10 times higher than the heat deformation temperature of the thermoplastic resin (A) used together.
-100 ° C, preferably 25-80 ° C, is selected and used. When the difference in the thermal deformation temperature between the thermotropic liquid crystal polyester and the thermoplastic resin is within the specified range, the thermotropic liquid crystal polyester acts as an anti-drip agent in the presence of an organic phosphorus compound containing no halogen element. It is thought to be. That is,
Thermotropic liquid crystal polyester reinforces the thermoplastic resin densely and firmly, prevents the formation of flammable low-molecular compounds inside the thermoplastic resin during combustion and reduces the viscosity, and a flame retardancy test (UL-94) It is considered that the prescribed drip can be prevented. If the difference between the thermal deformation temperatures of the thermotropic liquid crystal polyester and the thermoplastic resin is less than 10 ° C. or exceeds 100 ° C., a uniform dispersion state of the two cannot be obtained, and the thermotropic liquid crystal polyester does not show a drip prevention effect. .

Thermotropic liquid crystal polyester (B)
In consideration of the mechanical strength (particularly, toughness, etc.), flame retardancy, fluidity, etc. of the obtained flame-retardant resin composition, the amount used is usually 0 to 100 parts by weight of the thermoplastic resin (A). .01
The amount may be from 50 to 50 parts by weight, preferably from 0.1 to 40 parts by weight, more preferably from 0.5 to 30 parts by weight. If the amount is less than 0.01 part by weight, it is difficult to obtain a sufficient effect of improving the flame retardancy. On the other hand, if it exceeds 50 parts by weight, the amount of the relatively expensive thermotropic liquid crystal polyester increases, which is not preferable in terms of cost. Absent.

In the flame-retardant resin composition of the present invention,
(C) Examples of the organic phosphorus compound containing no halogen element include a phosphine compound containing no halogen element, a phosphine oxide compound containing no halogen element, a phosphate compound containing no halogen element, and a condensed phosphate containing no halogen element. At least one selected from compounds is used.

As the phosphine compound containing no halogen element, known compounds can be used, and examples thereof include trilaurylphosphine, triphenylphosphine, and tolylphosphine.

As the phosphine oxide compound containing no halogen element, known compounds can be used, and examples thereof include triphenylphosphine oxide and tolylphosphine oxide.

As the phosphoric ester compound containing no halogen element, known compounds can be used. For example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tricylyl phosphate, cresylate Zirdiphenyl phosphate,
Xylyl diphenyl phosphate, tolyl dixylyl phosphate, tris (nonylphenyl) phosphate,
(2-ethylhexyl) diphenyl phosphate, resorcinol diphenyl phosphate, hydroquinone diphenyl phosphate and the like can be mentioned.

As the condensed phosphate ester compound containing no halogen element, known compounds can be used. For example, resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), bisphenol-A bis (diphenyl phosphate), bisphenol- S bis (diphenyl phosphate), resorcinol bis (dixylyl phosphate), hydroquinone bis (dixylyl phosphate), bisphenol-A
Examples thereof include condensed phosphate compounds such as bis (ditolyl phosphate), bisphenol-A bis (dicylyl phosphate), and bisphenol-S bis (dicylyl phosphate).

Among these organic phosphorus compounds not containing a halogen element, aromatic phosphoric acid ester compounds such as triphenyl phosphate, tricresyl phosphate and trixylyl phosphate, resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate) , Bisphenol-A bis (diphenyl phosphate), resorcinol bis (dixylyl phosphate), hydroquinone bis (dixylyl phosphate), condensed phosphoric acid ester compounds such as bisphenol-A bis (ditolyl phosphate), triphenylphosphine oxide, tritolyl Phosphine oxide compounds such as phosphine oxide are preferable, and triphenyl phosphate, resorcinol bis (diphenyl phosphate), resorcinol Rubisu (dixylyl phosphate), triphenyl phosphine oxide, and the like are particularly preferable.

As the organic phosphorus compound containing no halogen element, one kind can be used alone, or two or more kinds can be used in combination.

The amount of the organophosphorus compound (C) containing no halogen element is determined in consideration of the mechanical strength (particularly, toughness, etc.) and flame retardancy of the obtained flame retardant resin composition. ) Usually 1 to 30 parts by weight per 100 parts by weight,
Preferably, it may be 5 to 20 parts by weight. If the amount is less than 1 part by weight, it is difficult to obtain a sufficient flame-retardant effect, while if it exceeds 30 parts by weight, the tendency to plasticize the resin is increased, and the mechanical and thermal properties are deteriorated.

In the flame-retardant resin composition of the present invention, the thermoplastic resin (A), thermotropic liquid crystal polyester (B) and the organic phosphorus compound (C) containing no halogen element are all powder, beads, flake,
Various shapes such as pellets can be used.

The flame-retardant resin composition of the present invention may contain various conventionally known resin additives and fillers as long as the preferable properties are not impaired.

As additives, for example, flame retardants other than organic phosphorus compounds containing no halogen element, ultraviolet absorbers,
Light stabilizer, antioxidant, light blocking agent, metal deactivator, quencher, heat stabilizer, lubricant, release agent, colorant, antistatic agent, antioxidant, plasticizer, impact strength improver, phase Solubilizers and the like can be mentioned.

Examples of the filler include mica, kaolin, talc, silica, clay, calcium carbonate, calcium sulfate, calcium silicate, glass beads, glass balloon, glass flake, glass fiber, and fibrous alkali metal titanate (titanium). Potassium fiber, etc.), fibrous transition metal borate (eg, aluminum borate fiber), fibrous alkaline earth metal borate (eg, magnesium borate fiber),
Zinc oxide whiskers, titanium oxide whiskers, magnesium oxide whiskers, gypsum whiskers, aluminum silicate whiskers, calcium silicate whiskers, silicon carbide whiskers, titanium carbide whiskers, silicon nitride whiskers, titanium nitride whiskers, carbon fibers, alumina fibers,
Alumina-silica fiber, zirconia fiber, quartz fiber, metal fiber and the like can be mentioned.

The additives and fillers may be used alone or in combination of two or more.

The flame-retardant resin composition of the present invention comprises a thermoplastic resin (A), a thermotropic liquid crystal polyester (B), and a predetermined amount of a halogen-free organic phosphorus compound (C), and if necessary. It can be produced by mixing and / or kneading additives and fillers by a known method. Each component may be mixed at once, or two or three types of components may be mixed and then the other components may be added and mixed sequentially. For mixing and / or kneading, an extruder such as a single-screw extruder or a twin-screw extruder, or a Banbury mixer, a pressure kneader,
A kneader such as a two-roll mill can be used.

The thus obtained flame-retardant resin composition of the present invention can be prepared by known methods such as injection molding, extrusion molding, vacuum molding, profile extrusion molding, blow molding, foam molding, injection press molding and gas injection molding. Depending on the molding method, a molded article of any shape can be obtained.

The flame-retardant resin composition of the present invention can be used for electricity, electronics, communications, agriculture, forestry and fisheries, mining, construction, food, textile, clothing,
It can be used in industrial fields such as medical, coal, petroleum, rubber, leather, automobile, precision equipment, wood, furniture, printing and musical instruments.

For example, printers, personal computers, word processors, keyboards, PDAs (small information terminals), telephones,
Facsimile, copier, ECR (electronic cash register),
Office / OA equipment such as calculators, electronic organizers, electronic dictionaries, cards, holders, stationery, etc., washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, kotatsu and other home appliances, TVs, VTRs, videos Cameras, boombox, tape recorders, minidiscs, CD players, speakers, AV equipment such as liquid crystal displays, connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor encapsulation materials, electric wires, cables, transformers, deflection yokes, minutes It can be used for applications such as electric and electronic parts such as electric boards and watches, and communication equipment. In addition, seats (filling, dressing, etc.), belts, ceiling covering, compatible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, wheel covers, mattress covers, airbags, insulating materials, suspenders, suspenders Obi, electric wire covering material, electric insulation material, paint, coating material, overlay material, floor material, corner wall, deck panel, covers, plywood, ceiling plate, partition plate, side wall, carpet, wallpaper, wall material, exterior Automobiles, vehicles, ships, aircraft and construction materials such as materials, interior materials, roofing materials, soundproofing boards, heat insulating boards, window materials, clothing, curtains, sheets, plywood, plywood, carpets, doormats, sheets, buckets It is suitable for use in daily life and sporting goods such as hoses, containers, glasses, bags, cases, goggles, skis, rackets, tents, musical instruments and the like.

[0055]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Synthesis Examples, Examples, Comparative Examples, and Test Examples. In each example,
“Parts” and “%” are based on weight unless otherwise specified. Synthesis Examples 1 to 9 (Synthesis of Thermotropic Liquid Crystal Polyester) Under a nitrogen atmosphere, a hydroxycarboxylic acid component, a diol component, and a dicarboxylic acid component are heated and melted and polycondensed to form a repeating structural unit represented by the following structural formula.

[0056]

Embedded image

Nine types of thermotropic liquid crystal polyesters having the composition shown in Table 1 were produced. Table 1 also shows the heat distortion temperature.

[0058]

[Table 1]

Synthesis Example 10 (resorcin-bis (2,6-
Synthesis of dimethylphenyl phosphate) A condenser connected with a stirrer, a thermometer and a water scrubber was attached to a four-necked flask, and 345 g of di (2,6-xylyl) phosphorochloridate and resorcinol 5 were attached thereto.
5 g and 1.5 g of aluminum chloride were added and mixed by heating, and the temperature of the reaction solution was gradually raised to 180 ° C. over 2 hours to carry out a dehydrochlorination reaction. After aging at the same temperature for 2 hours, the mixture was further aged at 200 mmHg under reduced pressure for 2 hours to complete the reaction. Xylene 500g, 10% hydrochloric acid aqueous solution 20
After adding 0 g, stirring to remove the remaining catalyst and the like, washing with water, the mixture was cooled to room temperature with stirring to precipitate crystals. The crystals are collected by filtration, washed with 200 g of methanol, and then washed with 100 g of methanol.
Drying under reduced pressure at a temperature of 330 ° C. yielded 330 g (96% yield) of white crystalline powder of resorcin-bis (2,6-dimethylphenyl phosphate). According to gel permeation chromatography analysis, the purity of the obtained crystals was 99%. 98-101 ° C. Synthesis Example 11 (Synthesis of hydroquinone-bis (di-2,6-xylyl phosphate)) A reaction was carried out in the same manner as in Synthesis Example 10 except that 55 g of hydroquinone was used instead of resorcinol, and hydroquinone-bis (di-2 326 g (95% yield, 99% purity) of a white powder crystal of (6-xylyl phosphate). Melting point 171-172 [deg.] C. Synthesis Example 12 (4,4-biphenylene-bis (di-2,6
Synthesis of -xylyl phosphate) The reaction was carried out in the same manner as in Synthesis Example 10 except that 93 g of 4,4-biphenol was used instead of resorcin, and 4,4-biphenol was reacted.
355 g of white powdery crystals of biphenylene-bis (di-2,6-xylyl phosphate) (93% yield, 99 purity)
%). 187-189 ° C. Examples 1 to 16 The twin screw extruder (trade name:
"S1-KRC 25mm Kneader", Inc.
Melting and kneading thermoplastic resin, thermotropic liquid crystal polyester ("liquid crystal polyester" in Table 2) and an organic phosphorus compound containing no halogen element ("organic phosphorus compound" in Table 2) using Kurimoto Iron Works. A pellet of the flame-retardant resin composition of the present invention was produced. The thermoplastic resins in Table 2 are as follows.

PC / ABS: manufactured by Mitsubishi Engineering-Plastics Corporation, trade name "Iupilon S-200"
0 "/ Mitsui Chemicals Co., Ltd., product name" Santac UT-6 "
1 "= 3/1 (weight ratio) mixture, heat distortion temperature 110 ° C.

PC / PBT: manufactured by Mitsubishi Engineering-Plastics Corporation, trade name "Iupilon S-200"
0 "/ Toray Industries, Inc., trade name" PBT-1200S "=
7/3 (weight ratio) mixture, heat deformation temperature 105 ° C.

PC: manufactured by Sumitomo Dow Co., Ltd., trade name "CAL"
BRE 300-10 ", heat distortion temperature 132 ° C.

PPE / HIPS: manufactured by Asahi Kasei Corporation, trade name “Zylon X-9108”, heat deformation temperature 110 ° C.

PPE / PA (polyamide): trade name “ARTLEY X-19S” manufactured by Sumitomo Chemical Co., Ltd., heat deformation temperature 120 ° C.

The thermotropic liquid crystal polyester “E321” in Table 2 indicates “Novaculate E321” (trade name, 175 ° C.) manufactured by Mitsubishi Chemical Corporation.

The following organic phosphorus compounds are shown in Table 2.

RBDX: Resorcinol obtained in Synthesis Example 10
Bis (2,6-dimethylphenyl phosphate).

HBDX: hydroquinone-bis (di-2,6-xylyl phosphate) obtained in Synthesis Example 11.

BBDX: 4,4-biphenylene-bis (di-2,6-xylyl phosphate) obtained in Synthesis Example 12.

TCP: tricresyl phosphate (manufactured by Wako Pure Chemical Industries, Ltd.).

TPP: triphenyl phosphate (manufactured by Wako Pure Chemical Industries, Ltd.).

TPPO: triphenylphosphine oxide (manufactured by Kanto Chemical Co., Ltd.). Comparative Examples 1 to 15 Resin composition pellets were produced in the same manner as in Examples 1 to 15, except that thermotropic liquid crystal polyester was not blended. Comparative Examples 16 to 18 In the same manner as in Examples 1 to 16, a thermoplastic resin having the compounding ratio (parts) shown in Table 2 and the following thermotropic liquid crystal polyester and an organic phosphorus compound were melt-kneaded, and a comparative resin composition was prepared. Manufactured.

LC3000 (Comparative Example 16): trade name “Rodrun LC3000”, manufactured by Unitika Ltd., heat deformation temperature 64 ° C.

A130 (Comparative Example 17): trade name “VECTRA A130”, manufactured by Polyplastics Co., Ltd., heat deformation temperature 240 ° C.

E6008 (Comparative Example 18): trade name “Econol E6008”, manufactured by Sumitomo Chemical Co., Ltd., heat distortion temperature 2
75 ° C.

[0076]

[Table 2]

In Table 2, the difference between the heat deformation temperatures is a value obtained by subtracting the heat deformation temperature of the thermoplastic resin from the heat deformation temperature of the liquid crystal polyester. Test Example 1 The pellets of the present invention and the comparative flame-retardant resin composition obtained in Examples 1 to 16 and Comparative Examples 1 to 18 were injected into an injection molding machine (trade name: "MINIMAT-26 / 15B", Sumitomo). A test piece was prepared by molding with Heavy Machinery Co., Ltd.) and evaluated by the following evaluation method.

1. Flexural modulus: JIS-K7203.

2. Thermal deformation temperature: Measured under a load of 18.6 kgf / cm ² using a molded article having a thickness of ８ inch and a width of 5 inches long according to ASTM D648.

3. Izod impact strength (IZ): JIS
-K7110, measured at 23 ° C.

4. Melt flow rate (MFR): JI
S-K7210 measured at 240 ° C with a load of 10 kgf.

5. Flame retardancy: UL-94 test method (Test f
or Flammability of Plastic Materials for Parts in
An evaluation test was performed using a test piece having a thickness of 1/16 inch, a length of 5 inches and a width of 0.5 inch based on Devices and Appliances UL-94, Fourth Edition). The evaluation criteria are as follows.

V-0: All of the following A to E are satisfied.

A: Each set of 5 test pieces was exposed to flame
Flaming (to keep burning with flame) is less than 10 seconds. B: Flaming after 10 times of flame contact, within 50 seconds, C: 5 pieces per set. Flaming of any specimen to clamp
No; D; none of the five test pieces in a set drip Flaming granules that ignite cotton 305 mm below; E; Glow none of the five test pieces in a set after the second flame contact
ing (flames and does not burn, but remains as a glowing fire) within 30 seconds.

V-1: All of the following A to E are satisfied.

A: Each set of five test pieces was exposed to flame
Flaming within 30 seconds, B; Flaming after 10 times of flame contact, 2 times for 5 pieces per set, within 250 seconds, C and D; same as V-0, E; 5 pieces per set All specimens were glowed after the second flame contact.
ing is within 60 seconds.

V-2: All of the following A to E are satisfied.

A, B, C, and E; Same as V-1. D; Flaming granules which ignite cotton 305 mm below at least one of five test pieces per set are dropped.

HB: In the horizontal test, none of the three test pieces per set burned up to the 101.6 mm mark after flame contact.

6. Drip property: During the flame retardancy test, the presence or absence of Flaming particles (drip) that ignite cotton was checked.

Table 3 shows the test results.

[0092]

[Table 3]

From Table 3, it can be seen that the flame retardant resin compositions of the present invention of Examples 1 to 16 have both flame retardancy and mechanical properties as compared with the comparative flame retardant resin compositions of Comparative Examples 1 to 18. It is clear that it is significantly better.

[0094]

According to the flame-retardant resin composition of the present invention, there is no problem caused by containing a halogen element.
It has excellent mechanical properties, moldability, and the like, and has a particularly remarkable effect that drip is unlikely to occur even if an anti-drip agent such as PTFE containing a halogen element is not blended.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 71/12 C08L 71/12 C09K 21/12 C09K 21/12 (72) Inventor Takashi Kameshima Ichikawa, Tokushima, Tokushima 463 Uchimachi Kasuno OTSUKA KOGYO CO., LTD.Tokushima Research Institute (72) Inventor Shinji Nakano KAKASUNO KAWAUCHI CHO, Tokushima City, Tokushima Pref. Tokushima Research Co., Ltd. (72) Inventor Yoichi NISHIOKA Kawachicho, Tokushima KU 463 Kagasuno, Otsuka Chemical Co., Ltd. Tokushima Research Laboratory (72) Inventor Hiroyuki Takase 463 Kagasuno, Kawauchi-machi, Tokushima City, Tokushima Pref. Otsuka Chemical Co., Ltd. Tokushima Research Laboratory F-term (reference) BC06W BC06X BN06W BN06X BN12W BN12X BN15W BN15X BN16W BN16X CF00W CF04W CF04Y CF05W CF06W CF07W CF08W CF08Y CF16Y CG00W CG01W CG02W CH07W EW046 EW136 EW146 GA00 GB00 GC00 GK00 GL00 GM00 GN00 GQ00

Claims (3)

[Claims] (A) 100 parts by weight of at least one thermoplastic resin selected from the group consisting of a polycarbonate resin, a polyphenylene ether resin, a polyester resin and a polystyrene resin, and (B) 0.01 to 50 thermotropic liquid crystal polyester. 1 to 30 parts by weight of (C) at least one halogen-free organic phosphorus compound selected from a phosphine compound, a phosphine oxide compound, a phosphate ester compound and a condensed phosphate ester compound which does not contain a halogen element (B)
Thermal deformation temperature of thermotropic liquid crystal polyester is
(A) 10 to 100 ° C. higher than the thermal deformation temperature of the thermoplastic resin
Highly flame-retardant resin composition. 2. The flame-retardant resin according to claim 1, wherein (A) the thermoplastic resin is a mixture of at least one selected from a polycarbonate resin, a polyphenylene ether resin and a polyester resin and a polystyrene resin. Composition. 3. Thermotropic liquid crystal polyester (B)
2. The heat distortion temperature of the pulp is about 100 to 200 ° C.
3. The flame-retardant resin composition according to item 1.