JP2002138182A - Flame-retardant resin composition and molding comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant resin composition having high flame- retardancy without using halogenated organic compound, with excellent mechanical strength and molding processability, and with excellent transparency in case applied to a transparent rubber reinforced styrenic resin, and to provide molding comprising it. SOLUTION: This flame-retardant resin composition comprises a phosphoric flame-retardant (B) and an epoxy compound (C) having weight average molecular weight of 1000 or lower and containing no halogen, added in a specified ratio to a rubber reinforced styrenic resin (A), exhibiting high flame-retardancy and excellent mechanical strength and molding processability, and further giving excellent transparency in case applied to a transparent rubber reinforced styrenic resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber-reinforced styrenic resin composition having excellent flame retardancy and a molded article comprising the same. Flame retardant resin composition having excellent flame resistance, excellent mechanical strength and moldability, and also excellent transparency when applied to a transparent rubber-reinforced styrene-based resin, and a molded article comprising the same. Things.

[0002]

2. Description of the Related Art Styrene resins typified by rubber-reinforced styrene resins have excellent mechanical properties, moldability, electrical insulation properties, and the like.
It is used in a wide range of fields including various parts such as OA equipment and automobiles. However, depending on the use, flame retardancy is required due to safety issues, and various techniques have been proposed for flame retardancy.

[0003] Generally, a method is employed in which a halogen-based flame retardant such as a bromine compound having a high flame-retardant efficiency and antimony oxide are blended with a resin to make the resin flame-retardant. However,
This method has problems such as a large amount of smoke generated during combustion.

[0004] Therefore, in order to overcome these drawbacks of halogen-based flame retardants, a flame-retardant resin containing no halogen has been strongly desired in recent years.

As a non-halogen flame retardant, there is a phosphorus flame retardant, and a phosphoric ester has been often used as a typical one. For example, a method of adding a polyphosphate to a thermoplastic resin (JP-A-59-24736),
A method of adding a phosphate having a specific structure to rubber-reinforced styrene (Japanese Patent Application Laid-Open No. H11-140270) and a method of adding a liquid phosphate to a styrene-based resin (Japanese Patent Application Laid-Open No. H11-5869) have already been disclosed. I have.

However, in the case of a thermoplastic resin which is inherently flammable, such as a styrene resin, the flame retarding effect of a phosphoric acid ester is extremely low.
In the compositions obtained by the methods described in JP-A-24736, JP-A-11-140270 and JP-A-11-5869, in order to impart flame retardancy to a thermoplastic resin, a large amount of a phosphate ester is used. Must be blended,
Therefore, not only the mechanical properties are reduced, but also the phosphate ester bleeds out, mold contamination occurs during molding, and a gas is generated during molding.

As a method for solving the above problems, a method using a hydroxyl group-containing phosphoric acid ester is disclosed in Japanese Patent Application Laid-Open No. Hei 5
-247315.

However, the phosphoric acid ester containing a hydroxyl group also has an extremely low flame retarding effect, and it has been difficult to solve the above problems.

[0009] Phosphate esters have a low flame retardant effect,
In order to improve the flame retardancy, we have found that flame retardancy is improved by using melamine cyanurate as a flame retardant aid in addition to the phosphate ester. The problem that the properties, impact resistance and moldability were impaired could not be solved.

In order to further improve the flame retardancy, a method of adding a novolak phenol resin and a compound having a triazine skeleton as a carbonized layer-forming polymer to a hydroxyl group-containing phosphate ester is disclosed in JP-A-7-704.
No. 48 discloses this.

This technique cannot solve the problem that the mechanical properties, impact resistance and moldability inherent in thermoplastic resins are impaired. Further, since phenol resin is a material having extremely poor light resistance, there is also a problem that the light resistance of the obtained resin composition is reduced.

[0012]

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, it is an object of the present invention to apply the present invention to a transparent rubber-reinforced styrene-based resin which has high flame retardancy without using a halogen-based organic compound, has excellent mechanical strength and moldability, and is excellent in molding properties. In such a case, the object is to provide a flame-retardant resin composition having excellent transparency and a molded article comprising the same.

[0014]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, by blending a phosphorus-based flame retardant and an epoxy compound with a rubber-reinforced styrene-based resin in a specific ratio, Having high flame retardancy, excellent mechanical strength and moldability, and when applied to a transparent rubber-reinforced styrene-based resin, a flame-retardant resin composition with excellent transparency can be obtained. The inventors have found that the present invention has been achieved.

That is, the flame-retardant resin composition of the present invention comprises:
100 parts by weight of a rubber-reinforced styrene resin (A), 1 to 30 parts by weight of a phosphorus-based flame retardant (B) and 0.1 to 10 parts by weight of a halogen-free epoxy compound (C),
The weight average molecular weight (Mw) of the epoxy compound (C) is 10
It is characterized by being equal to or less than 00.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the flame-retardant resin composition of the present invention and a molded article comprising the same will be described in detail.

The rubber-reinforced styrenic resin (A) in the present invention is a resin having a structure in which a (co) polymer containing a styrene monomer is grafted to a rubbery polymer and a resin containing a styrene monomer. (Co) polymers having a non-grafted structure to a rubbery polymer.

Such a rubber-reinforced styrenic resin (A)
For example, impact-resistant polystyrene (HIP
S), ABS resin (acrylonitrile-butadiene rubber-styrene copolymer), AAS resin (acrylonitrile-acryl rubber-styrene copolymer), MBS resin (methyl methacrylate-butadiene rubber-styrene copolymer), and AES resin ( Acrylonitrile-ethylene propylene rubber-styrene copolymer).

Specifically, in the presence of the rubbery polymer (e), an aromatic vinyl monomer (b), a vinyl cyanide monomer (c), and other copolymerizable with them. A graft copolymer (A-1) obtained by copolymerizing a monomer mixture comprising a vinyl monomer (d), an aromatic vinyl monomer (b), and a vinyl cyanide monomer (c) ) And a vinyl copolymer (A-2) comprising another vinyl monomer (d) copolymerizable therewith.

The graft copolymer (A-
The rubbery polymer (e) used in 1) is not particularly limited, but those having a glass transition temperature of 0 ° C. or lower are preferable.
Diene rubber, acrylic rubber, ethylene rubber and the like can be used. Specific examples of the rubbery polymer include polybutadiene, styrene-butadiene copolymer, styrene-butadiene block copolymer, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer, polyisoprene, and butadiene-methacrylic acid. Methyl copolymer, butyl acrylate-methyl methacrylate copolymer, butadiene-ethyl acrylate copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-isoprene copolymer and ethylene -Methyl acrylate copolymer and the like, among these rubbery polymers, polybutadiene, styrene-butadiene copolymer, styrene-butadiene block copolymer and acrylonitrile-butadiene copolymer, impact resistance Preferred in terms of Used.

The graft copolymer (A-
The weight average particle diameter of the rubbery polymer (e) constituting 1) is not particularly limited, but is preferably 0.1 to 2 μm, more preferably 0.2 to 1 μm in terms of impact strength. Is preferred.

The weight average particle size of the rubbery polymer is as follows:
"Rubber Age, Vol. 88, p. 484-
490, (1960), by E.E. Schmidt,
P. H. Biddison's sodium alginate method, that is, utilizing the fact that the particle size of polybutadiene to be creamed varies depending on the concentration of sodium alginate, the cumulative weight fraction of the creamed weight ratio and the cumulative weight fraction of the sodium alginate concentration are used. It can be measured by a method for obtaining a particle diameter of 50%.

These rubbery polymers (e) can be used in one kind or in a mixture of two or more kinds. However, when the rubbery polymer (e) is used in a mixture of two or more kinds, it is transparent. When imparting properties, the difference in refractive index measured using an Abbe refractometer is preferably 0.03 or less.

The graft copolymer (A-
The aromatic vinyl monomer (b) used for 1) and the vinyl copolymer (A-2) is not particularly limited, but styrene, α-methylstyrene, vinyltoluene, o-ethylstyrene, p- Although t-butylstyrene etc. are mentioned, styrene is especially preferable. These are one or two
More than one species can be used.

The graft copolymer (A-
The vinyl cyanide monomer (c) used for 1) and the vinyl copolymer (A-2) is not particularly limited, and includes acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like, and among them, acrylonitrile Is most preferably used. These can be used alone or in combination of two or more.

The other copolymerizable vinyl monomer (c) used for the graft copolymer (A-1) and the vinyl copolymer (A-2) in the present invention is an aromatic vinyl monomer. The monomer is not particularly limited as long as it can be copolymerized with the monomer (a) and the vinyl cyanide monomer (b), but the unsaturated carboxylic acid alkyl ester monomer (a) is preferable. Acrylate having an alkyl group or substituted alkyl group having 1 to 6 carbon atoms and / or
Or a methacrylic acid ester is preferable. As specific examples, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate,
N-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate,
2-chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,3,4, (meth) acrylate
Examples thereof include 5,6-pentahydroxyhexyl and 2,3,4,5-tetrahydroxypentyl (meth) acrylate, among which methyl methacrylate is preferred.
These can be used alone or in combination of two or more.

As other copolymerizable vinyl monomers (d), if necessary, (meth) acrylic acid,
Glycidyl (meth) acrylate, glycidyl itaconate, allyl glycidyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, maleic acid,
Maleic anhydride, monoethyl maleate, itaconic acid, itaconic anhydride, phthalic acid, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, acrylamide, methacrylamide, N-methylacrylamide, Butoxymethylacrylamide, N-propylmethacrylamide, aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene, 2-isopropenyl-oxazoline, 2- Cycloalkenyl - oxazoline, 2-acryloyl - oxazoline and 2-styryl - can also be used other copolymer available monomers such as oxazolines. These can be used alone or in combination of two or more.

The graft copolymer (A-
1) is a rubbery polymer (e) in the presence of 10 to 80 parts by weight, preferably 20 to 70 parts by weight, more preferably 30 to 60 parts by weight of an aromatic vinyl monomer (b) and cyanide. 20 to 90 parts by weight, preferably 30 to 80 parts by weight, more preferably 40 to 90 parts by weight of a monomer mixture of the vinylated monomer (c) and another vinyl monomer (d) copolymerizable therewith.
It is obtained by copolymerizing up to 70 parts by weight. When the proportion of the rubbery polymer (e) is less than 10 parts by weight or more than 80 parts by weight, impact strength and surface appearance may be reduced.

Further, in the present invention, when the rubber-reinforced styrenic resin has the following composition, it also has excellent transparency and flame retardancy. That is, in the presence of 10 to 80 parts by weight of the rubbery polymer (e), the rubber-reinforced styrene-based resin (A) is 50 to 90% by weight of an unsaturated carboxylic acid alkyl ester-based monomer (a), Group vinyl monomer (b)
10 to 50% by weight, vinyl cyanide monomer (c) 0
30% by weight and a monomer mixture 20 to 30% by weight of another vinyl monomer (d) copolymerizable therewith.
90 parts by weight of a graft copolymer (A-
1) 10 to 100 parts by weight, 50 to 90% by weight of unsaturated carboxylic acid alkyl ester monomer (a), 10 to 50% by weight of aromatic vinyl monomer (b), vinyl cyanide monomer 0 to 90 parts by weight of a vinyl copolymer (A-2) composed of 0 to 30% by weight of the body (c) and 0 to 30% by weight of another vinyl monomer (d) copolymerizable therewith. .

The graft copolymer (A-1) preferably has a graft ratio of 10 to 100% from the viewpoint of impact strength. Here, the graft ratio is a weight ratio of the grafted monomer mixture to the rubbery polymer. In addition, the graft copolymer (A-1) may include a non-grafted copolymer formed when the rubber mixture is graft-copolymerized with the monomer mixture. Methyl ethyl ketone solvent for ungrafted copolymer, 3
The intrinsic viscosity measured at 0 ° C. is not particularly limited, but is 0.1%.
Those having a thickness of 0.6 to dl / g are preferably used from the viewpoint of a balance between impact strength and moldability.

In the present invention, the vinyl copolymer (A-
Although the intrinsic viscosity measured at 30 ° C. in the methyl ethyl ketone solvent of 2) is not particularly limited, it is 0.2 to 1.0 dl / g.
Is preferably used from the viewpoint of a balance between impact strength and moldability, more preferably 0.3 to 0.7 d
1 / g.

The graft copolymer (A-
The method for producing 1) and the vinyl copolymer (A-2) are not particularly limited, and can be obtained by a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.

The mixing ratio of the graft copolymer (A-1) and the vinyl copolymer (A-2) constituting the rubber-reinforced styrene resin (A) of the present invention is preferably a graft copolymer. (A-1) 10 to 100 parts by weight, vinyl copolymer (A-2) 0 to 90 parts by weight, more preferably graft copolymer (A-1) 20 to 60 parts by weight, vinyl type The proportion of the copolymer (A-2) is from 0 to 80 parts by weight. If the amount of the graft copolymer (A-1) is less than 10 parts by weight, the impact resistance of the rubber-reinforced styrene resin (A) may be insufficient.

Further, the content of the rubbery polymer (e) contained in the rubber-reinforced styrenic resin (A) is preferably 5 to 30% by weight, more preferably 10 to 20% by weight. If the amount of the rubbery polymer (e) is less than 5% by weight, the impact resistance is insufficient, and if it exceeds 30% by weight, the moldability may be impaired, which is not preferable.

Here, when the rubber-reinforced styrene resin (A) is a rubber-reinforced styrene resin having transparency, the rubbery polymer (e) used for the graft polymer (A-1), Graft component and vinyl copolymer (A-
From the viewpoint of transparency, it is preferable to adjust the composition ratio of the monomers so that the difference between the refractive indices in 2) is 0.03 or less, more preferably 0.02 or less. In addition, such a graft polymer (A-1) and a vinyl copolymer (A-2) may be used in combination of two or more.

The flame-retardant resin composition of the present invention when applied to a transparent rubber-reinforced styrene resin has a total light transmittance of at least 60%, preferably at least 70%, more preferably at 23 ° C. Is desirably 80% or more. The total light transmittance here indicates a total light transmittance of a test piece having a thickness of 3 mm, and is measured at room temperature according to ASTM D-1003.

The phosphorus-based flame retardant (B) used in the present invention is not particularly limited as long as it is an organic or inorganic compound containing phosphorus. Examples thereof include ammonium polyphosphate, polyphosphazene, phosphate, phosphonate, phosphinate and Phosphine oxide and the like. Among them,
Polyphosphazenes and aromatic phosphates are preferred, and aromatic phosphates are particularly preferred.

Among the phosphorus-based flame retardants (B) used in the present invention, the aromatic phosphate is represented by the following general formula (3).

[0039]

Embedded image First, the structure of the flame retardant represented by the formula (3) will be described. In the formula (3), n is an integer of 0 or more, and may be a mixture of different n. K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less. Preferably, k and m are each an integer of 0 or more and 1 or less, particularly preferably k or m. Is 1.

In the formula (3), R ^{13 to} R ²⁰ represent the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms. Here, specific examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-
A butyl group and the like are mentioned, but hydrogen, a methyl group and an ethyl group are preferred, and hydrogen is particularly preferred.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different phenyl groups or phenyl groups substituted by halogen-free organic residues. Specific examples include a phenyl group, a tolyl group, a xylyl group, a cumenyl group,
Examples include a mesityl group, a naphthyl group, an indenyl group, an anthryl group, and the like. A phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a naphthyl group are preferable, and a phenyl group, a tolyl group, and a xylyl group are particularly preferable.

Y ⁴ is a direct bond, O, S, SO ₂ , C
(CH ₃ ) ₂ , CH ₂ , and CHPh, and Ph represents a phenyl group.

The amount of the phosphorus-based flame retardant (B) is usually 1 to 100 parts by weight of the rubber-reinforced styrene-based resin (A).
30 parts by weight, preferably 3 to 25 parts by weight, more preferably 5 to 20 parts by weight. If the amount of the phosphorus-based flame retardant (B) is less than 1 part by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 30 parts by weight, melt kneading with the resin composition may not be performed, and furthermore, molded articles This is not preferable because the mechanical properties and heat resistance may be greatly impaired.

The weight average molecular weight used in the present invention is 10
The epoxy compound (C) having a weight average molecular weight of 1000 or less and having two epoxy groups at the molecular terminals is preferably a compound having a weight average molecular weight of 1000 or less and having no more than 00, and having a formula represented by the following general formula (1). Are preferred.

[0045]

Embedded image First, the structure of the diepoxy compound represented by the formula (1) will be described. In the formula (1), R ^{1 to} R ⁴ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. Here, specific examples of the alkyl group having 1 to 5 carbon atoms include hydrogen, a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
Examples thereof include an tert-butyl group, and a methyl group and an ethyl group are preferable.

Y ¹ is a direct bond, O, S, SO ₂ , C
(CH ₃ ) ₂ , CH ₂ , C (CF ₃ ), CHPh;
h represents a phenyl group.

The weight average molecular weight used in the present invention is 10
A halogen-free epoxy compound (C) having a weight average molecular weight of 1,000 or less in the above general formula (1) and two epoxy groups at the molecular terminals Is preferable, and a compound represented by the following general formula (2) is preferable.

[0048]

Embedded image The structure of the diepoxy compound represented by the formula (2) will be described. In the formula (1), R ^{5 to} R ⁶ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. Here, specific examples of the alkyl group having 1 to 5 carbon atoms include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, ter
Although a t-butyl group etc. are mentioned, a methyl group and an ethyl group are preferable.

Y ² and Y ³ are a direct bond, O, S, S
O ₂ , C (CH ₃ ) ₂ , CH ₂ , C (CF ₃ ), and CHPh, and Ph represents a phenyl group.

In the present invention, the epoxy compound (C) includes, for example, glycidyl ether type, glycidyl ester type, glycidylamine type and alicyclic epoxy, but the glycidyl ether type is preferred.

Further, as a specific example of the glycidyl ether type epoxy resin, a bifunctional glycidyl ether type epoxy resin based on a phenol derivative is preferable because of its heat resistance, mechanical properties and cost reduction.
And epoxy resins such as bisphenol F type, bisphenol S type, bisphenol AF type, bisphenol AD type, biphenyl type, naphthalene type and fluorene type, and bisphenol A type is particularly preferable.

In the present invention, the weight average molecular weight is 1000
The following epoxy compound (C) has a weight average molecular weight of 10
When it exceeds 00, the flame retardancy is reduced, and when it is applied to a transparent rubber-reinforced styrenic resin, it is not preferable because the transparency is reduced. When the weight average molecular weight is less than 200, the mechanical properties are reduced. It is not preferable because As a preferable range of the weight average molecular weight, 300 to 800 are preferable because both flame retardancy and mechanical properties are satisfied, and when applied to a transparent rubber-reinforced styrene resin, good transparency is exhibited. More preferably, the weight average molecular weight is 30.
0 to 450.

The amount of the epoxy compound (C) having a weight average molecular weight of 1000 or less is 0.1 to 10 parts by weight, particularly 1 to 5 parts by weight, per 100 parts by weight of the rubber-reinforced styrene resin (A). Is preferably within the range. When added in excess of 10 parts by weight, heat resistance and impact resistance decrease,
Also, when applied to transparent rubber reinforced styrene resin,
This is not preferred because transparency is reduced.

The flame-retardant resin composition of the present invention is not particularly limited. However, 100 parts by weight of the rubber-reinforced styrene resin (A) and 5 to 15 phosphorus-based flame retardants (B) are used.
Parts by weight and a halogen-free epoxy compound (C)
1 to 3 parts by weight, and the weight average molecular weight (Mw) of the epoxy compound (C) is 300 to 800. When applied, it is preferable because it shows good transparency. More preferably, the phosphorus-based flame retardant (B) is 5 to 15 parts by weight based on 100 parts by weight of the rubber-reinforced styrene resin (A).
Parts by weight and a halogen-free epoxy compound (C)
The epoxy compound (C) has a weight average molecular weight (Mw) of 300 to 450 parts by weight.

Further, when the flame-retardant resin composition of the present invention is applied to a transparent rubber-reinforced styrene-based resin, a phosphite-based, hindered phenol-based, benzotriazole-based resin can be used as long as the transparency is not impaired. -Based, benzophenone-based, benzoate-based, and cyanoacrylate-based ultraviolet absorbers and antioxidants; higher fatty acids, acid esters, and acid amides; and lubricants and plasticizers such as higher alcohols; montanic acid and its salts and esters. , Half-esters, release agents such as stearyl alcohol, stearamide and ethylene wax, coloring inhibitors such as phosphites and hypophosphites, nucleating agents, amines, sulfonic acids, polyethers, etc. An additive such as an antistatic agent and a coloring agent such as a pigment may be contained.

The flame-retardant resin composition of the present invention is produced by a generally known method. For example, rubber-reinforced styrene resin (A), phosphorus-based flame retardant (B), weight average molecular weight of 1000
The following epoxy compound (C) and other desired additives are premixed or individually supplied to an extruder or the like without premixing, and sufficiently melted in a temperature range of 150 ° C to 300 ° C. It can be prepared by kneading. In this case, for example, a single-screw extruder equipped with a “Unimelt” type screw, a twin-screw extruder, a kneader of a kneader type and the like can be used. Particularly, in order to control the aspect ratio, a screw is used. It is preferable to use several kneading elements inserted or not inserted.

The flame-retardant resin composition of the present invention is excellent not only in flame retardancy but also in transparency, mechanical properties, impact resistance and moldability, and can be melt-molded. Extrusion molding, injection molding and press molding are possible,
It can be formed into films, tubes, rods and molded articles having any desired shape and size.

The molded article made of the flame-retardant resin composition of the present invention makes use of the excellent flame-retardant properties of the molded article for housings of electric / electronic parts, automobile parts, mechanical mechanism parts, OA equipment, home electric appliances and the like. It can be used for various applications such as parts and general goods.

Specific uses of the molded article comprising the flame-retardant resin composition of the present invention include, for example, housings for electric equipment, housings for OA equipment, various covers, various gears,
Various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups,
Oscillator, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, Parts or housings for parabolic antennas, computers, VTRs, televisions, irons, hair dryers, rice cookers, microwave ovens, audio equipment, etc., audio equipment parts or housings such as audio / laser disks (registered trademark) / compact disks, lighting, refrigerators , Air conditioners, typewriters, word processors, and other household and office electrical product parts or housings, office computer related parts, telephone related parts, facsimile related parts, copier related parts, etc. Or various bearings such as housings, cleaning jigs, oil-less bearings, stern bearings, underwater bearings, etc., motor parts, mechanical parts such as lighters, typewriters, microscopes, binoculars, cameras, watches, etc. Optical equipment, precision machinery related parts or housing, alternator terminal, alternator connector, IC regulator, various valves such as exhaust gas valve, fuel related / exhaust system / intake system various pipes, 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, thermostat base for air conditioner, heating hot air flow control valve, radiator Brush holder for motor, water pump impeller, turbine vane, parts related to wiper motor, dust distributor, starter switch, starter relay, wire harness for transmission,
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,
Examples include a lamp housing, a brake piston, a solenoid bobbin, an engine oil filter, and an ignition device case, which are extremely useful for these various applications.

[0060]

EXAMPLES Hereinafter, the structure and effects of the present invention will be described in more detail with reference to examples. This does not limit the invention.

In the following examples, a molding temperature of 230 using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., Ltd.
Each characteristic of the test piece obtained by injection molding at a temperature of 60 ° C. and a mold temperature of 60 ° C. was evaluated by the following measurement methods.

(1) Flame retardancy According to the evaluation standard defined in UL94, the thickness is 3.2
The flame retardancy was evaluated using a test piece of mm. The flame retardancy level decreases in the order of V-0>V-1>V-2> HB. In the case of the evaluation of V-2 or more, the sum of the first burning times of the five samples was used as an index of flame retardancy.

(2) Limiting oxygen index (LOI) According to the evaluation criteria defined in JIS K-7201, the limiting oxygen index is determined using a sample piece having a width of 6.5 ± 0.5 mm and a thickness of 3.0 ± 0.5 mm. (LOI) was measured.

(3) Heat resistance (DTUL) Heat resistance was evaluated in accordance with ASTM D-648 (load: 1.82 MPa).

(4) Impact Characteristics According to ASTM D-256, Izod impact strength was measured at 23 ° C. using a test piece (with a notch) having a thickness of 12.7 mm.

(5) Transparency Using a direct-reading haze meter manufactured by Toyo Seiki Co., Ltd.
The total light transmittance value (%) of a square plate having a thickness of 3 mm was measured at ℃.

Reference Example 1 Method for Producing Rubber-Reinforced Styrenic Resin (A) Method for Producing Graft Copolymer (A-1) Polybutadiene (weight average particle diameter 0.2 μm) 50 parts by weight (in terms of solid content) Olein 0.5 parts by weight of potassium acid 0.5 parts by weight of glucose 0.5 parts by weight of sodium pyrophosphate 0.005 parts by weight of ferrous sulfate 120 parts by weight of deionized water The above substances are charged into a polymerization vessel and stirred at 65 ° C. The temperature rose. The polymerization was started when the internal temperature reached 65 ° C., and 50 parts by weight of a mixture composed of 70 parts by weight of styrene, 30 parts by weight of acrylonitrile, and 0.3 part by weight of t-dodecylmercaptan were continuously dropped over 5 hours. 0.25 parts by weight of cumene hydroperoxide in parallel,
By continuously dropping an aqueous solution composed of 2.5 parts by weight of potassium oleate and 25 parts by weight of pure water over 7 hours,
The reaction was completed. The obtained graft copolymer latex is coagulated with sulfuric acid, neutralized with caustic soda, washed,
By filtration and drying, the graft copolymer (A-1-
1) was obtained.

Acetone was added to a predetermined amount (m) of the graft copolymer (A-1-1), and the mixture was refluxed for 4 hours. The solution was centrifuged at 8,800 rpm (centrifugal force 10,000 G) for 40 minutes. The insoluble matter was filtered. This insoluble content was reduced to 5 at 70 ° C.
After drying under reduced pressure for a period of time, the weight (n) was measured, and the graft ratio was 42%, which was calculated by the following formula: graft ratio = [(n) − (m) × L] / [(m) × L] × 100. there were. Here, L is the rubber content of the graft copolymer.

The filtrate of the acetone solution was concentrated by a rotary evaporator to obtain a precipitate (acetone-soluble matter). After drying this soluble matter under reduced pressure at 70 ° C. for 5 hours, 0.4
g / 100 ml (methyl ethyl ketone, 30 ° C.), and the intrinsic viscosity measured using an Ubbelohde viscometer is 0.1.
It was 37 dl / g.

In the same manner, 70 parts by weight of styrene and 30 parts by weight of acrylonitrile were changed to 70 parts by weight of methyl methacrylate, 25 parts by weight of styrene, and 5 parts by weight of acrylonitrile to obtain a graft copolymer (A-1). -2)
I got At this time, the graft ratio was 45%, and the intrinsic viscosity was 0.26 dl / g.

Production Method of Vinyl Copolymer (A-2) A methyl methacrylate / acrylamide copolymer (Japanese Patent Publication No. 45-2415) was placed in a stainless steel autoclave having a capacity of 20 L and equipped with a baffle and a Faudra type stirring blade.
A solution prepared by dissolving 0.05 part in 165 parts of ion-exchanged water was added, stirred at 400 rpm, and the system was replaced with nitrogen gas. Next, the following mixture was added while stirring the reaction system, and the temperature was raised to 60 ° C. to initiate polymerization.

70 parts by weight of styrene 30 parts by weight of acrylonitrile 0.2 part by weight of t-dodecylmercaptan 0.4 part by weight of 2,2′-azobisisobutyronitrile That is, the reaction temperature is raised to 65 ° C. in 15 minutes. After that, the temperature was raised to 100 ° C. over 50 minutes. Thereafter, cooling the reaction system, separating the polymer, washing,
Drying was performed to obtain a vinyl copolymer (A-2-1). The intrinsic viscosity of this vinyl copolymer (A-2-1) was 0.48 dl / g.

In the same manner, 70 parts by weight of styrene and 30 parts by weight of acrylonitrile were changed to 70 parts by weight of methyl methacrylate, 25 parts by weight of styrene, and 5 parts by weight of acrylonitrile to obtain a vinyl copolymer (A-2). -2) was obtained. The intrinsic viscosity of this vinyl copolymer (A-2-2) was 0.35 dl / g.

Reference Example 2 The phosphorus-based flame retardant (B) used in the present invention is as follows.

B-1: "PX-200" manufactured by Daihachi Chemical Co., Ltd.
(1,3-phenylenetetrakis (2,6-
B-2: "PX-201" (1,4-phenylenetetrakis (2,6-dimethylphenyl) phosphate) manufactured by Daihachi Chemical Co., Ltd., solid at 23 ° C. B- 3: "CR-733S" (resorcinol-bis (phenyl) phosphate oligomer) manufactured by Daihachi Chemical Co., Ltd.
Liquid at 3 ° C.

Reference Example 3 The epoxy compound (C) having a weight average molecular weight of 1,000 or less used in the present invention is as follows.

C-1: "RE-310S" manufactured by Nippon Kayaku Co., Ltd. A bisphenol A type epoxy resin represented by the following general formula (4): weight average molecular weight: about 342

[0078]

Embedded image C-2: “YX4000HK” manufactured by Nippon Kayaku Co., Ltd. Biphenyl type epoxy resin represented by the following general formula (5): Weight average molecular weight: about 360

[0079]

Embedded image C-3: "Epototo YD-134" manufactured by Toto Kasei Co., Ltd. Bisphenol A type epoxy resin represented by the following general formula (6): weight average molecular weight: about 500, polymerization degree: n ≒ 0.5

[0080]

Embedded image C-4: "Epototo YD-014" manufactured by Toto Kasei Co., Ltd. A bisphenol A type epoxy resin represented by the following general formula (6): a weight average molecular weight of about 1700, and a degree of polymerization n ≒ 4.4.

[0081]

Embedded image [Examples 1 to 7, Comparative Examples 1 to 9] Each component in accordance with the mixing ratio shown in Table 1 was prepared by using a screw having a screw diameter of 30 mm and an L / D of 25.
Co-rotating twin screw extruder (PCM-30 manufactured by Ikegai Iron Works)
And melt extruded at a resin temperature of 220 ° C. and a screw rotation speed of 150 rpm. After the obtained pellets were dried at 70 ° C. for 3 hours, they were subjected to injection molding to form target test pieces.

Table 2 shows the results of evaluating the physical properties of each test piece.

[0083]

[Table 1]

[0084]

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

That is, according to Comparative Examples 1 to 8, the addition of a phosphorus-based flame retardant and an epoxy compound
It has flame retardancy of V-2 or more as defined in the above, has a remarkable improvement in LOI, and is excellent in impact resistance and heat resistance. Further, when a transparent rubber-reinforced styrene resin is applied, a flame-retardant resin composition having excellent transparency can be obtained.

Further, those using the phosphorus-based flame retardant (B-1) alone (Example 1) are excellent from the viewpoint of balance between flame retardancy and mechanical properties. In the case of using the diepoxy compound (C-3) having a higher weight average molecular weight (Example 5), the flame retardancy is further improved, but the case where a transparent rubber-reinforced styrene resin is used (Example 8) ) Slightly reduces the transparency.

On the other hand, when the content of the rubbery polymer is too lower than the range of the present invention as in Comparative Example 1, the balance of physical properties is remarkably impaired in terms of impact properties and molding workability, and
-2 or higher flame retardancy may not be obtained.

When no phosphorus-based flame retardant was added as in Comparative Example 2, no flame retardancy was exhibited, and when excessive phosphorus-based flame retardant was added as in Comparative Example 3, The composition itself becomes remarkably brittle, and a good molded product cannot be obtained.

Further, when no epoxy compound was added as in Comparative Example 4, no flame retardancy was exhibited, and when an excessive amount of epoxy compound was added as in Comparative Example 5,
Not only does the drip during combustion worsen, the combustion time increases, but also the heat resistance and impact resistance deteriorate. Further, as in Comparative Example 6, when an epoxy compound (C-4) having a weight average molecular weight outside the range of the present invention is added, dripping during combustion is inhibited,
The burning time is prolonged, and flame retardancy of V-2 or more cannot be obtained.

When a transparent rubber-reinforced styrene resin is used, no flame retardancy is exhibited when no epoxy compound is added as in Comparative Example 7, and an excessive amount of epoxy resin is used as in Comparative Example 8. When a compound is added, the drip during combustion deteriorates, the combustion time is prolonged, and the heat resistance and impact resistance also deteriorate. Further, as in Comparative Example 9, an epoxy compound having a weight average molecular weight outside the range of the present invention (C-
When 4) is added, the burning time is prolonged and flame retardancy is not obtained, and the transparency is also deteriorated.

[0091]

As described above, according to the present invention,
A highly flame-retardant resin composition can be imparted to a rubber-reinforced styrene-based resin without using a halogen-based organic compound, and has excellent mechanical strength, impact resistance and moldability. be able to.

The flame-retardant resin composition obtained according to the present invention and a molded article comprising the same are suitable for applications such as housing and parts of general goods, electric equipment, OA equipment and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) // (C08L 51/04 (C08L 51/04 63:00) 63:00) AF term (Reference) 4F071 AA12 AA22 AA42 AA77 AA81 AC10 AC15 AE07 AF30 AF30Y BB03 BB05 BB06 BC01 BC05 BC06 BC07 4H028 AA35 AA42 BA06 4J002 BC031 BG061 BN061 BN071 BN121 BN151 BP011 CD032 CD05100 FD 010 FD FD FD FD 010 FD

Claims (8)

[Claims] (1) 100 parts by weight of a rubber-reinforced styrene resin (A), 1 to 30 parts by weight of a phosphorus-based flame retardant (B) and 0.1 to 10 parts by weight of a halogen-free epoxy compound (C). Wherein the epoxy compound (C) has a weight average molecular weight (Mw) of 1,000 or less. 2. The flame-retardant resin composition according to claim 1, wherein the epoxy compound (C) is a diepoxy compound. 3. An epoxy compound (C) having the following general formula (1):
The flame-retardant resin composition according to claim 1, wherein the resin composition is represented by: Embedded image (In the above formula, R ^{1 to} R ⁴ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. Y ¹ is a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , C (CF
₃ ) represents CHPh, and Ph represents a phenyl group. ) 4. An epoxy compound (C) having the following general formula (2)
The flame-retardant resin composition according to claim 1, wherein: Embedded image (In the above formula, R ^{5 to} R ¹² represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. Also, Y ² and Y ³
Is a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , C
(CF ₃ ) represents CHPh, and Ph represents a phenyl group. ) 5. The flame-retardant resin composition according to claim 1, wherein the total light transmittance measured at 23 ° C. is 60% or more. 6. The unsaturated carboxylic acid alkyl ester-based monomer (a) is added to the rubber-reinforced styrene resin (A) in the presence of 10 to 80 parts by weight of the rubbery polymer (e).
%, 10 to 50% by weight of an aromatic vinyl monomer (b), 0 to 30% by weight of a vinyl cyanide monomer (c), and another vinyl monomer (d) copolymerizable therewith. ) 0
Graft copolymer (A-1) obtained by copolymerizing 20 to 90 parts by weight of a monomer mixture consisting of 30% by weight.
Parts by weight, 50 to 90% by weight of an unsaturated carboxylic acid alkyl ester monomer (a), and an aromatic vinyl monomer (b)
10 to 50% by weight, vinyl cyanide monomer (c) 0
30% by weight and 0 to 90 parts by weight of a vinyl copolymer (A-2) composed of 0 to 30% by weight of another vinyl monomer (d) copolymerizable therewith. The flame-retardant resin composition according to claim 1. 7. The phosphorus-based flame retardant (B) represented by the following general formula (3)
The flame-retardant resin composition according to any one of claims 1 to 6, which is an aromatic phosphate represented by the following formula: Embedded image (In the above formula, R ^{13 to} R ²⁰ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.
r ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different phenyl groups or phenyl groups substituted with halogen-free organic residues. Y ⁴ is a direct bond, O, S,
Represents SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CHPh, and Ph represents a phenyl group. Further, n is an integer of 0 or more, and may be a mixture of different n. K and m are each 0 or more and 2
The following integers, and k + m is an integer of 0 or more and 2 or less. ) 8. A molded article comprising the flame-retardant resin composition according to any one of claims 1 to 7.