JP2001059046A - Flame retardant resin composition, its use and its molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame retardant styrene resin composition exhibiting high flame-retardancy without using a halogen-containing organic compound and having excellent mechanical properties and heat-resistance and provide its production process and molded article. SOLUTION: The objective flame retardant resin composition is produced by compounding 100 pts.wt. of a resin composition composed of (A) 20-98 pts.wt. of a styrene resin, (B) 1-40 pts.wt. of a styrene resin modified with a vinyl monomer containing epoxy group and (C) 1-40 pts.wt. of a polycarbonate resin with (D) 1-30 pts.wt. of a phenolic resin and (E) 1-10 pts.wt. of red phosphorus.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention has a high flame retardancy without using a halogenated organic compound,
The present invention relates to a flame-retardant styrenic resin composition having excellent mechanical properties and heat resistance, a method for producing the same, and a molded product thereof.

[0002]

2. Description of the Related Art Styrene resins typified by ABS resin and styrene / acrylonitrile copolymer resin (AS resin) have excellent moldability, surface appearance, mechanical properties, and the like. , OA equipment, automobiles, and other components.

[0003] However, styrene resins are extremely flammable among thermoplastic resins, and therefore, in many cases, flame retardancy is required from the viewpoint of safety.

As a method of imparting flame retardancy to a thermoplastic resin, a method of compounding a halogen-based organic compound as a flame retardant and an antimony compound as a flame-retardant auxiliary is generally used. In the case of a resin composition containing, there is a problem that a large amount of smoke is generated at the time of combustion. In view of recent environmental problems, it is strongly desired to realize a flame-retardant resin composition containing no halogenated organic compound. It is supposed to be.

On the other hand, as a method of making a thermoplastic resin flame-retardant without using a halogen-based organic compound, a method of adding a phosphoric ester-based flame retardant is generally used. Since a large amount of a flame retardant is required to impart the property, there is a problem that the mechanical properties and heat resistance of the resin composition are significantly reduced.

A method of adding red phosphorus as a flame retardant is disclosed in JP-A-58-108248, and a method of adding heat-expandable graphite and red phosphorus is disclosed in JP-A-9-296119.
In each of the above publications, the effect of improving the flame retardancy of the resin compositions obtained by these methods is small, and particularly, in the case of a styrene resin, the effect of improving the flame retardancy is insufficient. .

[0007]

SUMMARY OF THE INVENTION The present invention has been achieved as a result of studying to solve the problems in the prior art described above.

Accordingly, an object of the present invention is to provide a flame-retardant styrenic resin composition having a high level of flame retardancy without using a halogen-based organic compound and having excellent mechanical properties and heat resistance, and a method for producing the same. And a molded product thereof.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, they have been modified with a styrene resin (A) and a vinyl monomer containing an epoxy group. By blending the phenolic resin (D) and the red phosphorus (E) in specific amounts with respect to the resin composition composed of the styrene resin (B) and the polycarbonate resin (C), the resin composition has high flame retardancy, It has been found that a flame-retardant resin composition having excellent mechanical properties and heat resistance can be obtained.

That is, the flame-retardant resin composition of the present invention comprises:
20 to 98 parts by weight of a styrene resin (A), 1 to 40 parts by weight of a styrene resin (B) modified with a vinyl monomer having an epoxy group, 1 polycarbonate resin (C)
To 100 parts by weight of a resin composition consisting of ４０40 parts by weight,
1 to 30 parts by weight of phenolic resin (D), red phosphorus (E) 1
It is characterized by comprising a flame-retardant resin composition containing up to 7 parts by weight.

Further, the method for producing a flame-retardant resin composition of the present invention comprises a styrene resin (A), a styrene resin (B) modified with a vinyl monomer containing an epoxy group, and a polycarbonate resin (B). The phenolic resin (D) and the red phosphorus (E) are melt-kneaded with an extruder to the resin composition comprising C).

Further, the molded article of the present invention is characterized by comprising the above flame-retardant resin composition.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically.

The styrene resin (A) used in the present invention is a polymer containing an aromatic vinyl monomer as a main component. Specific examples of the aromatic vinyl monomer include styrene, α-methyl styrene, p-methyl styrene, vinyl toluene, t-butyl styrene, o
-Ethylstyrene, o-chlorostyrene and o, p-
Examples thereof include dichlorostyrene, and styrene and α-methylstyrene are particularly preferably used. These are 1
Species or two or more species may be used in combination.

For the purpose of imparting properties such as chemical resistance and heat resistance to the styrene resin, another vinyl monomer copolymerizable with the aromatic vinyl monomer may be copolymerized. .
Specific examples of these copolymerizable vinyl monomers include acrylonitrile, methacrylonitrile, ethacrylonitrile, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, ( N-propyl (meth) acrylate, n-butyl (meth) acrylate,
T-butyl (meth) acrylate, n (meth) acrylate
-Hexyl, chloromethyl (meth) acrylate, glycidyl (meth) acrylate, maleic anhydride, itaconic anhydride, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and the like, In particular, acrylonitrile is preferably used.

The ratio of the aromatic vinyl monomer in the styrene resin is from 50 to 100 from the viewpoint of moldability.
% By weight, especially 60-90% by weight. At the same time, the weight average molecular weight of the styrene resin in terms of polystyrene is 5
It is preferable to use one having a mass of 300,000 to 300,000 in order to maintain the balance of physical properties. The weight average molecular weight referred to here is determined by gel permeation chromatography (hereinafter referred to as G
PC (abbreviated as PC) in a generally known manner.

Further, in order to improve the impact resistance of the styrene resin, it is preferable to use a rubber-modified styrene resin in which rubbery polymer particles are dispersed in a styrene resin. Here, as the rubbery polymer to be used, a polymer or copolymer containing a conjugated diene as a main component is preferable.
Among them, the content of the conjugated diene is 60% by weight or more, especially 7%.
It is preferably at least 5% by weight. Specifically, polybutadiene rubber, styrene-butadiene copolymer, hydrogenated styrene-butadiene rubber, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer, isoprene rubber, and the like can be used.

Here, since the rubbery polymer and the styrene resin as the matrix are incompatible with each other, if a component compatible with the matrix is grafted onto the rubbery polymer, the impact resistance can be further improved. Can be. That is, it is preferable to use a graft copolymer obtained by graft-polymerizing an aromatic vinyl monomer and another monomer copolymerizable therewith in the presence of the rubbery polymer. As each monomer, it is preferable to use the same components as the styrene-based resin as the matrix in the same ratio.The composition and the amount of grafting are not particularly limited, but the dispersibility of the rubbery polymer is not limited. It is preferable to adjust the composition and the graft amount so as not to impair.

Specific examples of the above styrene resin include:
Polystyrene, high impact polystyrene, styrene / acrylonitrile copolymer resin (AS resin), modified A
S resin, acrylonitrile / acrylic rubber / styrene copolymer resin (AAS resin), acrylonitrile / ethylene propylene rubber / styrene copolymer resin (AES resin), ABS resin, etc., from the viewpoint of flame retardancy, A containing acrylonitrile as a copolymer component and having excellent balance between mechanical properties and moldability
S resins, ABS resins and modified AS resins are preferred.

The method for producing the styrene resin is not particularly limited, and it can be produced by a conventionally known method. That is, it can be produced by any method of emulsion polymerization, solution polymerization, bulk polymerization and suspension polymerization, but bulk polymerization is industrially advantageous.

As for the method of grafting an aromatic vinyl monomer and another monomer copolymerizable therewith to the rubbery polymer, conventionally known emulsion polymerization or bulk polymerization may be employed. Although it is possible, the production method by emulsion polymerization is advantageous in quality.

The styrene resin may be used alone or in combination of two or more obtained by the above method.

The amount of the styrene resin (A) in the present invention is 20 to 98 parts by weight, preferably 30 to 80 parts by weight, and more preferably 4 to 100 parts by weight based on 100 parts by weight of the resin composition.
0 to 70 parts by weight. If the styrene-based resin (A) is less than 20 parts by weight, the fluidity may be reduced and the moldability of the styrene-based resin may be impaired. If it exceeds 98 parts by weight, sufficient flame retardancy may not be obtained. Not preferred.

The styrene resin (B) modified with a vinyl monomer containing an epoxy group used in the present invention is:
A copolymer obtained by copolymerizing a monomer mixture consisting of an aromatic vinyl monomer, a vinyl monomer containing an epoxy group, and another vinyl monomer copolymerizable therewith. .

Here, the aromatic vinyl monomer includes:
One or more selected from the specific examples of the aromatic vinyl-based monomer used in the styrene-based resin (A) can be used, and among them, styrene can be preferably used.

The vinyl monomer containing an epoxy group is a compound having both a vinyl polymerizable radical group and an epoxy group in one molecule, and specific examples thereof include:
(Meth) glycidyl acrylate, glycidyl ethacrylate, glycidyl esters of unsaturated organic acids such as glycidyl itaconate, glycidyl ethers such as allyl glycidyl ether, and the above-mentioned derivatives such as 2-methylglycidyl methacrylate, among others. (Meta)
Glycidyl acrylate can be preferably used. These may be used alone or in combination of two or more.

Specific examples of the other monomers copolymerizable with the above include other monomers copolymerizable with an aromatic vinyl monomer used in the styrene resin (A). And at least one selected from the group consisting of acrylonitrile and acrylonitrile.

In the styrene resin (B) modified with a vinyl monomer containing an epoxy group and composed of the above-mentioned copolymer component, the copolymerization amount of the vinyl monomer containing an epoxy group is as follows: Preferably 0.001 to 14% by weight,
More preferably, it is 0.01 to 5% by weight.

There is no particular limitation on the production of the styrene resin (B) modified with a vinyl monomer containing an epoxy group, and it can be produced by any of emulsion polymerization, solution polymerization, bulk polymerization and suspension polymerization. can do.

The amount of the styrenic resin (B) modified with an epoxy group-containing vinyl monomer in the present invention is from 1 to 40 parts by weight, preferably from 5 to 35 parts by weight, per 100 parts by weight of the resin composition. Parts by weight, more preferably 10 to 30 parts by weight
Parts by weight. If the styrene resin (B) modified with a vinyl monomer containing an epoxy group is less than 1 part by weight,
Flame retardancy and mechanical properties are insufficient, and if it exceeds 40 parts by weight, the fluidity is remarkably deteriorated, and the excellent moldability of the styrene resin may be impaired.

The polycarbonate resin (C) used in the present invention is a polymer obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester. Having a viscosity average molecular weight of 10,000 to 1,000
It is preferably in the range of 000.

Here, specific examples of the dihydric phenol compound include 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxy-3,5
-Dimethylphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy −3,5-
Diphenyl) butane, 2,2-bis (4-hydroxy-
3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane and 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane and the like, which can be used alone or as a mixture.

The amount of the polycarbonate resin (C) in the present invention is 1 to 100 parts by weight of the resin composition.
It is 40 parts by weight, preferably 5 to 35 parts by weight, more preferably 10 to 30 parts by weight. If the polycarbonate resin (C) is less than 1 part by weight, the flame retardancy and mechanical properties are insufficient, and if it exceeds 40 parts by weight, the fluidity is significantly deteriorated,
It is not preferable because the excellent processability of the styrene resin may be impaired.

The flame-retardant thermoplastic resin composition of the present invention comprises the styrene resin (A) described above, a styrene resin (B) modified with a vinyl monomer containing an epoxy group, and a polycarbonate resin (C). A phenolic resin (D) and red phosphorus (E) are added to 100 parts by weight of the resin composition consisting of

Here, the phenolic resin (D) used in the present invention is not particularly limited as long as it is a polymer having a plurality of phenolic hydroxyl groups. For example, novolak type, resol type and heat reaction type resins, or Modified resins are mentioned. These are uncured resins with no hardener added,
It may be a semi-cured resin or a cured resin. Among them,
A phenol novolak resin which does not contain a curing agent and is non-reactive is preferred in terms of flame retardancy and economy. Also,
The shape of the phenol resin is not particularly limited, and any of crushed products, granules, flakes, powders, needles, and liquids can be used.

Although the molecular weight of the phenolic resin is not particularly limited, the number average molecular weight in terms of polystyrene is 200 to 200.
2,000, and particularly those in the range of 400 to 1,500 are preferably used from the viewpoint of moldability and economic efficiency. The number average molecular weight of the phenolic resin can be measured by a GPC method using a tetrahydrafuran solution.

The above-mentioned phenolic resin may be optionally used
Species or two or more can be used.

The amount of the phenolic resin (D) used in the present invention is 1 to 100 parts by weight of the resin composition.
The amount is 30 parts by weight, preferably 3 to 20 parts by weight, more preferably 5 to 10 parts by weight. If the phenolic resin (D) is less than 1 part by weight, sufficient flame retardancy may not be obtained, and if it exceeds 30 parts by weight, the mechanical properties of the resin composition may be impaired.

The red phosphorus (E) used in the present invention is unstable as it is, and has a property of gradually dissolving in water or reacting with water gradually. Those that have been used are preferably used. As a method for treating such red phosphorus, as described in JP-A-5-229806, a crushed surface having high reactivity with water or oxygen is formed on the surface of red phosphorus without pulverizing the red phosphorus. A method of finely dispersing red phosphorus without causing it, a method of catalytically suppressing oxidation of red phosphorus by adding a small amount of aluminum hydroxide or magnesium hydroxide to red phosphorus, coating red phosphorus with paraffin or wax, and Method of suppressing contact with, stable method by mixing with ε-caprolactam and trioxane, stable by coating red phosphorus with thermosetting resin such as phenolic, melamine, epoxy and unsaturated polyester Method of treating red phosphorus with an aqueous solution of a metal salt such as copper, nickel, silver, iron, aluminum and titanium to precipitate and stabilize a metal phosphorus compound on the surface of red phosphorus Aluminum hydroxide, magnesium hydroxide red phosphorus,
Titanium hydroxide, a method of coating with zinc hydroxide and the like, a method of stabilizing by coating the surface of red phosphorus with electroless plating with iron, cobalt, nickel, manganese, tin, and the like, and a method of combining these, Preferably, a method of pulverizing red phosphorus without forming a crushed surface on the surface of the red phosphorus without pulverizing the red phosphorus, heat curing the red phosphorus such as a phenol-based, melamine-based, epoxy-based, unsaturated polyester-based, etc. A method in which red phosphorus is stabilized by coating with a hydrophilic resin, and a method in which red phosphorus is stabilized by coating with aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide, or the like. A method of pulverizing red phosphorus without pulverizing and forming a crushed surface on the surface, converting red phosphorus into phenolic, melamine, epoxy, unsaturated polyester, etc. A method combining method or the both of them to be stabilized by coating with a curable resin. Among these thermosetting resins, red phosphorus coated with a phenolic thermosetting resin or an epoxy thermosetting resin can be preferably used in terms of moisture resistance,
Particularly preferred is red phosphorus coated with a phenolic thermosetting resin. In addition, unmilled red phosphorus refers to red phosphorus produced without forming a crushed surface.

Among such red phosphorus, it is particularly preferable that the red phosphorus is not pulverized, and the red phosphorus is finely divided without forming a crushed surface having high reactivity with water or oxygen on the surface of the red phosphorus. Red phosphorus coated with a phenol-based thermosetting resin or an epoxy-based thermosetting resin is most preferable.

The average particle size of red phosphorus before being blended with the resin is 0.00 from the viewpoints of flame retardancy, mechanical properties, and chemical and physical deterioration of red phosphorus due to grinding during recycling.
1 to 35 μm is preferable, and more preferably,
It is 0.1 to 30 μm.

The average particle size of red phosphorus can be measured by a general laser diffraction type particle size distribution analyzer. There are two types of particle size distribution analyzers: wet method and dry method.
Either one may be used. In the case of the wet method, water can be used as a dispersion solvent for red phosphorus. At this time, red phosphorus surface treatment may be performed with an alcohol or a neutral detergent. It is also possible to use phosphates such as sodium hexametaphosphate and sodium pyrophosphate as the dispersant.

Red phosphorus having a large particle diameter contained in red phosphorus, that is, red phosphorus having a particle diameter of 75 μm or more significantly reduces flame retardancy, mechanical properties and recyclability. Therefore, red phosphorus having a particle size of 75 μm or more is preferably removed by classification or the like. The content of red phosphorus having a particle size of 75 μm or more is from the viewpoint of flame retardancy, mechanical properties and recyclability.
10% by weight or less, more preferably 8% by weight
Or less, particularly preferably 5% by weight or less. The lower limit is not particularly limited, but is preferably as close to 0 as possible.

Here, the particle diameter contained in the red phosphorus is 75 μm.
The above-mentioned red phosphorus content can be measured by classification using a 75 μm mesh. That is, 100 g of red phosphorus
The content of red phosphorus having a particle diameter of 75 μm or more is A / 100 × 10
It can be calculated from 0 (%).

The conductivity of the red phosphorus (E) used in the present invention when extracted in hot water (where the conductivity is red phosphorus 5).
g, add 100 mL of pure water, extract in an autoclave at 121 ° C. for 100 hours, dilute the filtrate after red phosphorus filtration to 250 mL, and measure the conductivity of the extracted water.)
Is the moisture resistance, mechanical strength, electrical properties,
From the viewpoint of recyclability and usually 0.1 to 1000 μ
S / cm, preferably 0.1 to 800 μS / c
m, more preferably in the range of 0.1 to 500 μS / cm.

Preferred commercial products of red phosphorus include "NOVA EXCEL 140" and "NOVA EXCEL F5" manufactured by Rin Kagaku Kogyo KK and equivalents of these commercial products.

The amount of red phosphorus (E) in the present invention is 1 to 10 parts by weight, preferably 2 to 7 parts by weight, based on 100 parts by weight of the resin composition. If the amount of red phosphorus (E) is less than 1 part by weight, the flame retardancy is insufficient. If the amount exceeds 10 parts by weight, the resin composition itself becomes brittle and practical mechanical properties may not be obtained. It is not preferable because there is.

In the present invention, it is preferable to use a compatibilizer (F) for the purpose of further improving mechanical properties and flame retardancy.

The compatibilizer is a polymer (A) obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester in the same molecule and a polymer mainly composed of an aromatic vinyl monomer. (B). Further, a graft polymer containing polycarbonate (a) as a main component and a polymer (b) mainly containing an aromatic vinyl monomer as a branch component can be preferably used. Such a graft polymer is prepared by reacting a polymer having a functional group capable of binding to a trunk component at one end of a molecular chain serving as a branch component with the trunk component, or in the presence of two types of polymers. And a method in which a radical generator such as a peroxide is blended and melt-kneaded.

The polymer mainly composed of an aromatic vinyl monomer is not particularly limited. However, in order to enhance the compatibility with the styrene resin (A), other copolymerizable vinyl monomers may be used. It is preferred to copolymerize the body. Further, as specific examples of the aromatic vinyl monomer and the other copolymerizable vinyl monomer, one or more kinds can be selected from the specific examples that can be used in the styrene resin (A). preferable.

Regarding the amount of the compatibilizer (F) to be added,
In order to further enhance the effect of improving impact resistance and flame retardancy, it is advantageous to use 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the resin composition.

The flame-retardant resin composition of the present invention may further contain carbon black and a colorant. Here, the carbon black and the colorant are pigments that can be generally blended with a thermoplastic resin.
0.01 to 30 parts by weight with respect to 00 parts by weight, and 0.05 to 1 part by weight from the viewpoints of toning property, flame retardancy and mechanical properties.
It is preferably added in the range of 0 parts by weight.

The flame-retardant resin composition of the present invention may contain a phosphorus-based, phenol-based stabilizer, a phenol-based, phosphite-based or sulfur-based antioxidant, depending on the purpose.
Hindered phenol-based, benzotriazole-based, benzophenone-based, benzoate-based and cyanoacrylate-based UV absorbers, waxes, lubricants and plasticizers such as higher fatty acids, acid esters, and acid amides, and higher alcohols, amines, and sulfones An acid-based or polyether-based antistatic agent or the like can be added.

The flame-retardant resin composition of the present invention is produced by a generally known method. That is, a styrene resin (A),
A method of melt-kneading a styrene resin (B), a polycarbonate resin (C), a phenol resin (D), red phosphorus (E) and other necessary additives modified with a vinyl monomer containing an epoxy group. There is no particular limitation, and any method and apparatus capable of performing mechanical shearing in a molten state of a styrene-based resin such as a single-screw extruder, a twin-screw extruder, and a kneader may be used. Preferably, an extruder that can be manufactured continuously,
In particular, the use of a twin-screw extruder is advantageous in terms of productivity. It is also preferable to provide a vent for the purpose of removing water and low-molecular-weight volatile components generated during melt-kneading.

Here, when an extruder is used, the final extruder is preferably used from the viewpoints of productivity, operability, dispersibility of red phosphorus, flame retardancy of the flame retardant resin composition obtained, and mechanical properties. A part of the resin component and the whole or part of the red phosphorus (E) are once melt-kneaded to produce a resin composition (G) having a high red phosphorus concentration, and the remaining resin component, a phenol resin (D) ), A resin composition (G) having a high red phosphorus concentration, and if necessary, other additives that can be optionally used are melt-kneaded with an extruder.

Alternatively, a part of the resin component finally blended, red phosphorus (E) and other optional additives can be melt-kneaded once and actually blended into the flame-retardant resin composition. A resin composition (G) having a higher concentration of red phosphorus than the amount of red phosphorus to be produced is produced, and a resin composition having a higher concentration of red phosphorus (G) and, if necessary, a resin composition having a higher concentration of red phosphorus. It is prepared by melt-kneading additives other than the optional additives added in the production stage of the product (G).

As a specific example of the "part of the resin component finally mixed", a part or all of the styrene resin (A) is modified with a vinyl monomer containing an epoxy group. Part or all of the styrene resin (B) or part or all of the polycarbonate resin (C) can be exemplified. In particular, a high-concentration product of red phosphorus composed of the polycarbonate resin (C) is most effective for exerting the effects of the present invention, and can greatly improve the handling property of red phosphorus, which is conventionally dangerous. Can be used as a flame retardant for styrene resins. The composition of the flame retardant for a styrene resin is preferably 10 to 200 parts by weight of red phosphorus (E) based on 100 parts by weight of the polycarbonate resin (C).

As described above, at the stage of producing the resin composition (G) having a higher red phosphorus concentration than the amount of red phosphorus to be actually blended into the flame retardant resin composition, any other optional use may be made. When a possible additive is blended, it is preferable that these optional additives are mixed in advance with red phosphorus.

The resin composition having a high red phosphorus concentration (G)
Is preferably used in the form of a so-called master pellet, but is not limited thereto, and may be in the form of a chip, a powder, or a mixture thereof.

The flame-retardant resin composition thus obtained can be molded by generally known methods such as injection molding, extrusion molding and compression molding, and can be used to form molded articles of any shape such as molded articles, sheets and films. Can be. Among them, it is particularly suitable for use in injection molded products. It is also suitable for molded products having complicated shapes such as molded products having welds and hinges and insert molded products, and thin-walled molded products. These molded products can be used as various mechanical mechanism parts, electric / electronic parts or automobile parts. It is suitable.

For example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors,
Variable condenser case, optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, housing, semiconductor, liquid crystal display parts, FDD carriage , FDD chassis, HDD parts, motor brush holders, parabolic antennas, electrical and electronic parts such as computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio parts・ Sound equipment parts such as laser discs and compact discs, lighting parts,
Home, office electrical product parts, office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, oilless bearings, such as refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. , Stern bearings, underwater bearings and other bearings, motor parts, mechanical parts such as lighters and typewriters, optical equipment such as microscopes, binoculars, cameras, watches, etc., precision machinery parts, alternator terminals, Alternator connector, I
C regulator, potentiometer base for light deer, various valves such as exhaust gas valve, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer , Exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, thermostat base for air conditioner, heating hot air flow control valve, radiator motor Brush holder, water pump impeller, turbine vane, wiper motor related parts, dust distributor , Starter switch, starter relay, transmission wire harness,
Window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation board, step motor rotor, lamp socket, lamp reflector,
It is useful for various applications such as lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition cases, play equipment, toiletries, recreational supplies, toys, chemical plants, aviation parts, etc. Utilizing the features of the invention, it can be used as parts for electric home appliances, OA equipment and housings, and automobile parts.

[0062]

EXAMPLES Hereinafter, the structure and effect of the present invention will be described in more detail with reference to examples.

The measuring method of each characteristic is as follows.

(1) Flame Retardancy A test piece for evaluating flame retardancy obtained by injection molding using an IS55EPN injection molding machine manufactured by Toshiba Machine at a molding temperature of 250 ° C. and a mold temperature of 60 ° C. UL94
The flame retardancy was evaluated according to the evaluation criteria set forth in. The thickness of the test piece is 3.2 mm, and the flame retardancy level is V-0> V-
1>V−2> HB. In the case of the evaluation of V-0 or more, the sum of the burning times of the five samples was used as an index of flame retardancy.

(2) Mechanical Properties A 1/4 inch thick test piece obtained by injection molding at a molding temperature of 250 ° C. and a mold temperature of 60 ° C. using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd. , A
The flexural modulus and flexural stress were measured according to STM D-790.

(3) Impact Characteristics A 1/4 inch thick test piece (notch) obtained by injection molding using an IS55EPN injection molding machine manufactured by Toshiba Machine at a molding temperature of 250 ° C. and a mold temperature of 60 ° C. Attached)
Was measured for Izod impact strength according to ASTM D-256.

(4) Heat Resistance A 1/4 inch thick test piece obtained by injection molding using an IS55EPN injection molding machine manufactured by Toshiba Machine at a molding temperature of 250 ° C. and a mold temperature of 60 ° C. A
According to STM D-648 (load: 1.82 MPa),
The deflection temperature under load (DTUL) was measured.

Reference Example 1 The styrenic resins (A-1, A-2) used in the present invention were prepared as follows.

A-1: A monomer composed of 70 parts by weight of styrene and 30 parts by weight of acrylonitrile was subjected to suspension polymerization in a polymerization tank equipped with a stirrer to prepare a styrene resin. After sufficiently drying the obtained bead-shaped resin, it was dissolved in methyl ethyl ketone, and the intrinsic viscosity was measured in a thermostat at 30 ° C .. As a result, it was 0.50 dl / g.

A-2: A polybutadiene rubber and a styrene-butadiene rubber latex are charged into a glass reaction vessel, and while stirring, glucose, sodium pyrophosphate and ferrous sulfate dissolved in ion-exchanged water are charged in predetermined amounts. The temperature inside the reaction vessel was raised to 65 ° C.

To this mixture, a monomer mixture consisting of styrene, acrylonitrile and t-dodecylmercaptan, and an aqueous solution of cumene hydroperoxide in potassium oleate were separately dropped successively to give 95% by weight of the monomer. The polymerization was completed when the above polymerization was completed.

The obtained graft polymer latex was coagulated with sulfuric acid, neutralized with sodium hydroxide, washed with water, dehydrated and dried to obtain a graft polymer powder. The content (L) of the rubbery polymer in the graft polymer was 50%.

Acetone was added to a predetermined amount M (g) of the obtained graft polymer powder, and the mixture was refluxed at about 70 ° C. for 4 hours. After the solution was centrifuged at 9,000 rpm for 30 minutes, insoluble components were filtered. This insoluble matter was dried under reduced pressure at 60 ° C. for 5 hours, and the weight N (g) was measured. The graft ratio G (%) represented by the following equation was 40%. G = 100 × (N−M × L) / (M × L) Further, in the above acetone solution, after filtering the insoluble matter, acetone was evaporated from the filtrate, and methanol was added to the residue to polymerize the polymer. Extracted. After the extract was dried under reduced pressure at 60 ° C. for 3 hours, it was dissolved in methyl ethyl ketone, and the solution was measured for intrinsic viscosity in a 30 ° C. constant temperature bath.
It was 35 dl / g.

Reference Example 2 A styrene resin (B) modified with an epoxy group-containing vinyl monomer used in the present invention was prepared as follows.

In a polymerization tank equipped with a stirrer, styrene 7
A monomer composed of 5.5 parts by weight, acrylonitrile 24 parts by weight, and glycidyl methacrylate 0.5 part by weight was subjected to suspension polymerization to prepare a modified styrene resin. After sufficiently drying the obtained bead-shaped resin, dissolved in methyl ethyl ketone,
The intrinsic viscosity was measured in a thermostat at 30 ° C.
It was 60 dl / g.

Reference Example 3 The contents of the polycarbonate resin (C) used in the present invention are as follows. C: Mitsubishi Chemical polycarbonate resin "Iupilon S3000".

Reference Example 4 The phenolic resin (D) used in the present invention is as follows. Sumitomo Durez phenolic novolak resin "PR531"
95 ".

Reference Example 5 The contents of red phosphorus (E) used in the present invention are as follows. The conductivity was determined by adding 100 mL of pure water to 5 g of red phosphorus, extracting in an autoclave at 121 ° C. for 100 hours, filtering red phosphorus, and filtering the filtrate to 25%.
It was diluted to 0 mL and measured using a conductivity meter (Yokogawa Electric's personal SC meter).

E-1: Red phosphorus “Nova Excel 140” manufactured by Rin Kagaku Kogyo Co., Ltd. Average particle size 30 μm, conductivity 200 μS / cm E-2: Red phosphorus “Nova Red 120” manufactured by Rin Kagaku Kogyo Co., Ltd. Average particle size 38 μm, conductivity 1200 μS / cm, particle size 7
Red phosphorus content of 5 μm or more 15%.

Reference Example 6 The red phosphorus high concentration resin components (G-1 to G-3) used in the present invention were prepared as follows.

G-1: polycarbonate resin (C) 10
0 parts by weight, 25 parts by weight of red phosphorus (E-1) was mixed, and a screw diameter of 30 mm, L
Melt extrusion at a resin temperature of 270 ° C using a coaxial rotary twin screw extruder with a /D=45.5 (manufactured by Nippon Seiko Co., Ltd., TEX-30). Was prepared.

G-2: polycarbonate resin (C) 10
25 parts by weight of red phosphorus (E-2) was mixed with 0 parts by weight, and a high concentration product of a polycarbonate resin having a red phosphorus concentration of 20% by weight was prepared in the same manner.

G-3: Nylon resin (H) 10 described below
25 parts by weight of red phosphorus (E-1) was mixed with 0 parts by weight, and a high-concentration red phosphorus-containing nylon resin having a red phosphorus concentration of 20% by weight was prepared in the same manner.

[Reference Example 7] The nylon resin (H) used in the present invention is as follows. H: Toray nylon resin "Amilan CM101
0 ".

[Reference Example 8] The compatibilizer (F) used in the present invention is as follows.

"MODIPA CH-430" manufactured by NOF Corporation is a graft copolymer obtained by grafting polycarbonate as a main component and an AS resin as a branch component.

[Examples 1 to 5, Comparative Examples 1 to 6] According to the compounding ratios shown in Table 1, each component was prepared with a screw diameter of 30 mm, L
/ D is 25 co-rotating twin-screw extruder (Ikegai Iron Works PC
M-30), and the resin temperature 2
Melt extrusion was performed at 50 ° C. and a screw rotation speed of 150 rpm. The obtained pellet was dried at 70 ° C. for 3 hours, and then subjected to injection molding to form a target test piece. Table 2 shows the results of evaluating the physical properties of the test pieces.

[0088]

[Table 1]

[0089]

[Table 2] The following is clear from the examples and comparative examples in Tables 1 and 2.

Composition comprising styrene resin (A), modified styrene resin containing epoxy group (B), polycarbonate resin (C), phenol resin (D) and red phosphorus (E) of Examples 1 to 5 The object is V-0 specified in UL94
It can be seen that the above flame retardancy was obtained, and that it had excellent flame retardancy, flexural modulus, bending stress, impact resistance and heat resistance as compared with Comparative Examples 1 to 6.

In particular, from the comparison between Example 1 and Comparative Example 1 and between Example 2 and Comparative Example 2, it is clear that the addition of the styrene-based resin (B) containing an epoxy group improves the flammability.

From Examples 2 and 3 and Comparative Example 3, a decrease in flame retardancy is apparent with a decrease in the amount of the phenolic resin (D). The desired flame retardancy of the present invention can be obtained without the addition of the phenolic resin. I can't.

From Examples 2 and 4, it is clear that the addition of the compatibilizer (F) shortens the combustion time and improves the Izod impact strength. Average particle size 3 from Examples 2 and 5
The use of red phosphorus (E-1) having 0 μm and a conductivity of 200 μS / cm is advantageous because the burning time is short.

In Comparative Example 4, since the content of the styrene-based resin (B) containing an epoxy group is excessive, the extrusion / moldability is inhibited by gelation, and a molded article can be obtained by the production method under the above conditions. Did not.

In Comparative Example 5, since the added amount of red phosphorus (E) was excessive, the Izod impact was extremely low and practical mechanical strength could not be obtained.

As can be seen from Comparative Example 5, when the nylon resin (H) was used instead of the polycarbonate resin (C), the intended flame retardancy was not obtained.

[0097]

As described above, the flame-retardant resin composition of the present invention has high flame retardancy without using a halogenated organic compound, and at the same time, exhibits excellent mechanical properties and heat resistance. I do.

The flame-retardant resin composition obtained according to the present invention and a molded article comprising the same can be suitably used for applications such as home appliances, office automation equipment, automobile parts and housings.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) C08L 61/06 C08L 61/06 69/00 69/00 F term (reference) 4J002 BC031 BC061 BC071 BC081 BC091 BC122 BH011 BH021 BN121 BN141 BN151 BN161 CC044 CC074 CD192 CG013 DA056 FB076 FB266 FD136

Claims (6)

[Claims] 1. A styrene resin (A) in an amount of 20 to 98 parts by weight,
A phenolic resin is added to 100 parts by weight of a resin composition comprising 1 to 40 parts by weight of a styrene resin (B) modified with a vinyl monomer having an epoxy group and 1 to 40 parts by weight of a polycarbonate resin (C). A flame-retardant resin composition comprising (D) 1 to 30 parts by weight and red phosphorus (E) 1 to 10 parts by weight. 2. The flame-retardant resin composition according to claim 1, wherein the styrene resin (A) is a rubber-modified styrene resin. (3) a polycarbonate as a main component,
The compatibilizer (F) comprising a graft polymer having a styrene-based resin as a branch component was added in an amount of 0.1 to 100 parts by weight of the resin composition.
The flame-retardant resin composition according to claim 1, wherein the composition is contained in an amount of 1 to 20 parts by weight. 4. The red phosphorus (E) has a conductivity of 0.1 to 100.
The flame-retardant resin composition according to any one of claims 1 to 3, wherein the composition is 0 µS / cm. 5. A resin composition (G) having a high red phosphorus concentration is prepared by melt-kneading a part of the resin component to be finally mixed and the whole or a part of the red phosphorus (E), and then preparing the remaining resin composition. The method for producing a flame-retardant resin composition according to any one of claims 1 to 4, wherein the resin component (A) and the resin composition (G) having a high red phosphorus concentration are melt-kneaded in an extruder. 6. A molded article comprising the flame-retardant resin composition according to claim 1.