JP2001139742A - Flame-retardant resin composition, its production and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant resin composition, having a highly flame- retardant property without using a halogen-based organic compound, and at the same time excellent in mechanical properties and flame-retardant property, its method of production and molded product. SOLUTION: This flame-retardant resin composition is obtained by compounding (D) 1-30 pt.wt. phenol-based resin and (E) 1-10 pt.wt. red phosphorus into 100 pts.wt. resin composition consisting of (A) 20-98 pt.wt. styrene resin, (B) 1-40 pt.wt. modified styrene resin copolymerized with an epoxy group- containing vinyl-based monomer and (C) 1-40 pt.wt. polyester resin.

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 resin with 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 an organic compound, there is a problem that a large amount of smoke is generated at the time of combustion. Therefore, in connection with recent environmental problems, realization of a flame-retardant resin composition containing no halogenated organic compound has been realized. Is becoming increasingly desirable.

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.
However, the effect of improving the flame retardancy is small in the resin compositions obtained by these methods, especially when the styrene resin is to be made flame retardant by this method. The effect of improving the properties was 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 As a result of intensive studies to achieve the above object, the present inventors have found that a modified styrene obtained by copolymerizing a styrene resin (A) and an epoxy group-containing vinyl monomer. By blending specific amounts of the phenolic resin (D) and red phosphorus (E) with the resin composition composed of the base resin (B) and the polyester resin (C), it has high flame retardancy, and 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:
Styrene resin (A) 20 to 98 parts by weight, modified styrene resin (B) 1-4 copolymerized with epoxy group-containing monomer
To 100 parts by weight of a resin composition comprising 0 parts by weight and 1 to 60 parts by weight of a polyester resin (C), 1 to 30 parts by weight of a phenolic resin (D) and 1 to 10 parts by weight of red phosphorus (E) are blended. It is characterized by becoming.

In the flame-retardant resin composition of the present invention, the styrene-based resin (A) is a rubber-modified styrene-based resin, and the conductive properties of the red phosphorus (E) when extracted in hot water. Rate (5 g of red phosphorus, 100 ml of pure water was added thereto, and extracted in an autoclave at 121 ° C. for 100 hours, for example).
That the filtrate after red phosphorus filtration is diluted to 250 ml and the conductivity of the extracted water is in the range of 0.1 to 1000 μS / cm;
It is preferable that the content of red phosphorus having a particle size of 75 μm or more in the red phosphorus (E) is 10% by weight or less.

Further, the method for producing a flame-retardant resin composition of the present invention comprises the above-mentioned styrene resin (A), a modified styrene resin (B) obtained by copolymerizing an epoxy group-containing vinyl monomer, and a polyester resin (B). At least a part of the resin component selected from C) and the whole or a part of the red phosphorus (E) are once melt-kneaded to produce a resin composition (F) having a high red phosphorus concentration, and then the remaining resin composition (F) is manufactured. The resin component and the resin composition (F) having a high red phosphorus concentration are melt-kneaded in an extruder.

In the method for producing a flame-retardant resin composition according to the present invention, at least a part of the polyester resin (C) and the whole or a part of the red phosphorus (E) are once melt-kneaded and mixed. After producing the resin composition (F) having a high concentration, it is preferable that the remaining resin component and the resin composition (F) having a high red phosphorus concentration are melt-kneaded with an extruder.

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

[0015]

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 (A) is from 50 to 50 from the viewpoint of moldability.
100% by weight, especially 60-90% by weight, is preferred. The polystyrene-equivalent weight average molecular weight of the styrene resin (A) is preferably in the range of 50,000 to 300,000 for maintaining the balance of physical properties. The weight average molecular weight mentioned here can be measured by a generally known technique using gel permeation chromatography (hereinafter abbreviated as GPC).

As the styrenic resin (A), it is preferable to use a rubber-modified styrenic resin in which rubbery polymer particles are dispersed in a styrenic resin in order to improve the impact resistance. 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, particularly preferably 75% by weight or more. 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.

Since the rubbery polymer and the styrenic 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 styrene resin (A) include polystyrene, high impact polystyrene, styrene / acrylonitrile copolymer resin (AS resin),
Modified AS resin, acrylonitrile / acrylic rubber / styrene copolymer resin (AAS resin), acrylonitrile /
Ethylene propylene rubber / styrene copolymer resin (AE
S resin) and ABS resin. From the viewpoint of flame retardancy, AS resin, ABS resin, and modified AS resin containing acrylonitrile as a copolymer component and having excellent balance between mechanical properties and moldability. Resins are preferred.

The method for producing the styrene resin (A) is not particularly limited, and it can be produced by a conventionally known method. That is, it can be produced by any method such as 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 (A) may be used alone or in combination of two or more obtained by the above method.

The mixing ratio of the styrene resin (A) in the present invention is 20 to 98 parts by weight, preferably 30 to 80 parts by weight, more preferably 40 to 70 parts by weight, per 100 parts by weight of the resin composition. By setting the blending ratio of the styrene resin (A) in the range of 20 to 98 parts by weight, sufficient flame retardancy can be obtained without impairing the moldability.

The modified styrenic resin (B) obtained by copolymerizing an epoxy group-containing vinyl monomer used in the present invention is an aromatic vinyl monomer, an epoxy group-containing vinyl monomer and a copolymer thereof. It is a copolymer obtained by copolymerizing a monomer mixture composed of another polymerizable vinyl monomer.

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

The epoxy group-containing vinyl monomer is a compound having both a vinyl group and an epoxy group which can be radically polymerized in one molecule. Specific examples thereof include glycidyl (meth) acrylate and ethacrylic acid. Glycidyl esters of unsaturated organic acids such as glycidyl and glycidyl itaconate; glycidyl ethers such as allyl glycidyl ether; and the above-mentioned derivatives such as 2-methylglycidyl methacrylate are preferable. Among them, glycidyl (meth) acrylate is preferable. Can be used. These may be used alone or in combination of two or more.

Further, as other monomers copolymerizable with these, specific examples of the other monomers copolymerizable with the aromatic vinyl monomer used in the styrene resin (A) are given. One or more selected from the examples can be used, and among them, acrylonitrile can be preferably used.

In the modified styrenic resin (B) composed of the above-mentioned copolymerized components and copolymerized with an epoxy group-containing vinyl monomer, the copolymerization amount of the epoxy group-containing vinyl monomer is preferably 0. 0.001 to 14% by weight, more preferably 0.01 to 5% by weight.

The production of the modified styrenic resin (B) obtained by copolymerizing an epoxy group-containing vinyl monomer is not particularly limited, and may be carried out by any method such as emulsion polymerization, solution polymerization, bulk polymerization and suspension polymerization. Can be manufactured.

In the present invention, the blending ratio of the modified styrene resin (B) obtained by copolymerizing an epoxy group-containing vinyl monomer is 1 to 40 parts by weight, preferably 5 to 35 parts by weight, per 100 parts by weight of the resin composition. Parts, more preferably 10 to 30 parts
Parts by weight. By adjusting the blending amount of the modified styrene resin (B) obtained by copolymerizing an epoxy group-containing vinyl monomer in the range of 1 to 40 parts by weight, the flame retardancy and mechanical properties are sufficiently satisfied, and the fluidity is improved. It is possible to obtain a thermoplastic resin composition that does not cause deterioration in moldability due to deterioration.

The polyester resin (C) used in the present invention is an aromatic polyester having an aromatic ring in a chain unit of a polymer, specifically, an aromatic dicarboxylic acid,
Alternatively, it is a polymer or copolymer obtained by a polycondensation reaction between the ester derivative and a diol component.

Here, the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-
Naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,2′-biphenyldicarboxylic acid, 3,3′-biphenyldicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4 '-
Diphenyl ether dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 4,4'-diphenyl isopropylidene dicarboxylic acid, 1,2-bis (phenoxy) ethane-
4,4′-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 4,4 ′
Examples thereof include -p-terphenylenedicarboxylic acid and 2,5-pyridinedicarboxylic acid. Of these, terephthalic acid can be preferably used.

These aromatic dicarboxylic acids may be used alone or in combination of two or more. In addition, if it is a small amount, one or two or more of these aromatic dicarboxylic acids may be used together with adipic acid, azelaic acid, dodecandioic acid, aliphatic dicarboxylic acids such as sebacic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. May be used in combination.

The diol component includes ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol,
Examples include aliphatic diols such as 2-methyl-1,3-propanediol, diethylene glycol and triethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, and mixtures thereof. In addition, if it is a small amount, even if one kind or two or more kinds of long chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like are copolymerized. Good.

Specific examples of the polyester resin (C) include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene-1,2-bis (phenoxy) ethane-4,4'-.
In addition to dicarboxylate, copolymerized polyesters such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, and polybutylene terephthalate / decane dicarboxylate are exemplified. Of these, polybutylene terephthalate and polyethylene terephthalate can be preferably used.
The polyester resin (C) used in the present invention is:
The relative viscosity of a 0.5% o-chlorophenol solution measured at 25 ° C. is 1.15 to 3.0, especially 1.3 to 2.5.
Are preferred.

The mixing ratio of the polyester resin (C) in the present invention is 1 to 60 parts by weight, preferably 5 to 40 parts by weight, more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the resin composition.
0 to 30 parts by weight. By setting the blending ratio of the polyester resin (C) in the range of 1 to 60 parts by weight, the flame retardancy is satisfied, the warpage and molding shrinkage after molding are small, and the styrene resin (A) is excellently molded. A flame-retardant resin composition that does not impair workability can be obtained.

The flame-retardant resin composition of the present invention comprises the above-mentioned styrene resin (A), modified styrene resin (B) obtained by copolymerizing an epoxy group-containing vinyl monomer, and polyester resin (C). With respect to 100 parts by weight of the resulting resin composition,
Further, a phenolic resin (D) and red phosphorus (E) are blended.

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. Above all, a phenol novolak resin which does not contain a curing agent and is non-thermally reactive is preferable in terms of flame retardancy and economy. The shape of the phenol resin is not particularly limited,
Any of granules, flakes, powders, needles, and liquids can be used.

The molecular weight of the phenolic resin (D) is not particularly limited, but may be 20 in terms of polystyrene equivalent number average molecular weight.
A range of 0 to 2,000, particularly a range of 400 to 1,500 is preferably used from the viewpoints of moldability and economy. In addition, the number average molecular weight of the phenolic resin (D) can be measured by a GPC method of a tetrahydrafuran solution.

The phenolic resin (D) can be used alone or in combination of two or more as required.

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. By setting the amount of the phenolic resin (D) to be in the range of 1 to 30 parts by weight, a flame-retardant resin composition having sufficient flame retardancy can be obtained without impairing mechanical properties.

The red phosphorus (E) used in the present invention is unstable as it is, and has the 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, etc., a method of stabilizing the surface of red phosphorus by electroless plating with iron, cobalt, nickel, manganese, tin, and the like, and a method of combining these methods. ,Preferably,
A method of pulverizing red phosphorus without forming a crushed surface on the surface of red phosphorus without pulverizing the red phosphorus, using a thermosetting resin such as a phenolic, melamine, epoxy, or unsaturated polyester resin A method of stabilizing by coating, a method of stabilizing by coating red phosphorus with aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide, etc., and particularly preferably, pulverizing red phosphorus. A method of forming red phosphorus into fine particles without forming a crushed surface on the surface, and a method of stabilizing red phosphorus by coating it with a thermosetting resin such as a phenolic, melamine, epoxy, or unsaturated polyester resin Alternatively, it is a method combining these two. Among these thermosetting resins, red phosphorus coated with a phenolic thermosetting resin or an epoxy thermosetting resin can be preferably used from the viewpoint of moisture resistance, and particularly preferably a phenolic thermosetting resin. Red phosphorus coated with a resin can be preferably used. In addition, unmilled red phosphorus means red phosphorus produced without forming a crushed surface.

Among such red phosphorus (E), the red phosphorus is pulverized without pulverization of the red phosphorus and 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 (E) before being blended in the resin composition is selected from the viewpoints of flame retardancy, mechanical properties, and suppression of chemical and physical deterioration of red phosphorus due to pulverization during recycling. , 0.01 to 35 μm, particularly preferably 0.1 to 30 μm.

The average particle size of red phosphorus (E) can be measured by a general laser diffraction type particle size distribution analyzer. The particle size distribution measuring apparatus includes a wet method and a dry method, and any method 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.

Further, red phosphorus having a large particle diameter contained in red phosphorus (E), 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 preferably 10% by weight or less, more preferably 8% by weight or less, and particularly preferably 5% by weight or less, in view of flame retardancy, mechanical properties and recyclability. The lower limit is not particularly limited, but is preferably as close to 0% by weight.

Here, the particle size contained in the red phosphorus (E) is 7
The red phosphorus content of 5 μm or more can be measured by classification with a 75 μm mesh. That is, red phosphorus 1
Residual amount A when 00g is classified with a 75 μm mesh
According to (g), the content of red phosphorus having a particle size of 75 μm or more is A / 10
It can be calculated from 0 × 100 (%).

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 in 100 ml of pure water, and extracted in an autoclave at 121 ° C. for 100 hours, and the filtrate obtained after red phosphorus filtration is diluted to 250 ml) to determine the moisture resistance of the obtained molded product. From the viewpoint of mechanical strength, electrical properties, and recyclability, it is usually 0.1 to 1000 μS / cm, preferably 0.1 to 800 μS / cm, more preferably 0.1 to 500 μS / cm.

Commercial products of such preferred red phosphorus (E) include “NOVA EXCEL 140” manufactured by Rin Kagaku Kogyo Co., Ltd.
“Nova Excel F5” and equivalents thereof to commercially available products may be mentioned.

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. The addition amount of red phosphorus (E) is 1 to 1
When the amount is in the range of 0 parts by weight, it is possible to obtain a flame-retardant resin composition having sufficient flame retardancy and not causing a decrease in mechanical properties due to embrittlement.

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 from the viewpoint of toning property, flame retardancy and mechanical properties, 0.05 to 30 parts by weight.
It is preferably added in the range of 10 parts by weight.

The flame-retardant resin composition of the present invention may contain, depending on the purpose, phosphorus-based, phenol-based stabilizers, phenol-based, phosphite-based and sulfur-based antioxidants,
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),
Melt kneading of modified styrene resin (B), polyester resin (C), phenol resin (D), red phosphorus (E) and other necessary additives obtained by copolymerizing an epoxy group-containing vinyl monomer. Is not particularly limited, as long as it is a method / apparatus capable of mechanically shearing a styrene-based resin in a molten state, such as a single-screw extruder, a twin-screw extruder, or a kneader. Preferably, the use of an extruder that can be manufactured continuously, particularly 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. At least a part of the resin component and the whole or a part of the red phosphorus (E) are once melt-kneaded to produce a resin composition (F) having a high red phosphorus concentration, and then the remaining resin component , A phenolic resin (D), a resin composition (F) having a high red phosphorus concentration, and, if necessary, other optional additives can be melt-kneaded with an extruder.

Alternatively, at least 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 (F) having a higher red phosphorus concentration than the amount of red phosphorus to be produced is prepared, and then the remaining resin component is added with a red phosphorus-rich resin composition (F) and, if necessary, a red phosphorus concentration. It is prepared by melt-kneading additives other than the optional additives added in the production stage of the high resin composition (F).

Specific examples of the “part of the resin component to be finally mixed” include a part or all of the styrene resin (A) and a modified styrene obtained by copolymerizing an epoxy group-containing vinyl monomer. Part or all of the system resin (B) or part or all of the polyester resin (C) can be exemplified. Particularly, a high-concentration product of red phosphorus comprising the polyester resin (C) is most advantageous for exhibiting the effects of the present invention, and dramatically improves the handling of red phosphorus which has been regarded as a dangerous substance. Therefore, it can be preferably used as a flame retardant for styrene resins. The composition of the flame retardant for a styrene-based resin is as follows: 100 parts by weight of the polyester resin (C) and 10 to 200 parts of red phosphorus (E).
It is preferably in parts by weight.

As described above, in the step of producing the resin composition (F) having a higher red phosphorus concentration than the amount of red phosphorus to be actually blended into the flame-retardant resin composition, other optional use may be made. When a possible additive is blended, it is preferable to mix these optional additives with red phosphorus in advance.

The resin composition (F) having a high red phosphorus concentration
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 of the present invention thus obtained can be molded by generally known methods such as injection molding, extrusion molding and compression molding, and molded articles of all shapes such as molded articles, sheets and films. It 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.

Specific uses of the molded article obtained from the flame-retardant resin composition of the present invention include, for example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, Coil bobbin, condenser, variable condenser case, optical pickup,
Oscillator, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystal display parts,
Electric / electronic parts such as FDD carriage, FDD chassis, HDD parts, motor brush holder, parabolic antenna, computer related parts, etc .; VT
R parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, audio parts, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts Home and office electrical product parts, office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, oil-less bearings, stern bearings, underwater bearings, and other various bearings and motors Machine-related parts such as parts, lighters, typewriters, etc., optical equipment such as microscopes, binoculars, cameras, clocks, etc., precision machine-related parts, alternator terminals, alternator connectors, IC regulators, potentiometers for light drier Over scan, various valves such as exhaust gas valve, fuel related-exhaust system, an 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, brake butt wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, 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 rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, igniter cases, play equipment, toiletry supplies, recreational supplies, toy supplies, chemical plants, aviation parts, etc. However, among the above, it can be preferably used as a part for electric home appliances, OA equipment, a housing, and an automobile part by utilizing the features of the present invention.

[0063]

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. is 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 1.6 mm, and the flame retardancy level decreases in the order of 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 using an IS55EPN injection molding machine manufactured by Toshiba Machine at a molding temperature of 250 ° C. and a mold temperature of 60 ° C.
The flexural modulus and flexural stress were measured according to STM D-790. (3) Impact characteristics A 1/4 inch thick test piece (with a notch) obtained by injection molding using a Toshiba Machine's IS55EPN injection molding machine at a molding temperature of 250 ° C and a mold temperature of 60 ° C.
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 a Toshiba Machine's IS55EPN injection molding machine at a molding temperature of 250 ° C. and a mold temperature of 60 ° C.
According to STM D-648 (load: 1.82 MPa),
The deflection temperature under load (DTUL) was measured. [Reference Example 1] The styrene resin (A-1,
A-2) was prepared as follows.

A-1: A monomer comprising 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 A-1. 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 latex of polybutadiene rubber and styrene-butadiene rubber was charged into a glass reactor, and while stirring, glucose, sodium pyrophosphate and ferrous sulfate dissolved in ion-exchanged water were 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-dodecyl mercaptan, and an aqueous solution of cumene hydroperoxide in potassium oleate were separately dropped continuously 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 (styrene resin A-2) powder. The content (L) of the rubbery polymer in the graft polymer was 50% by weight.

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 form a 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 0.35 dl / g. Reference Example 2 A styrene resin (B) modified with an epoxy group-containing vinyl monomer used in Examples was prepared as follows.

In a polymerization vessel equipped with a stirrer, styrene 7
A monomer composed of 5.5 parts by weight, 24 parts by weight of acrylonitrile, and 0.5 part by weight of glycidyl methacrylate was subjected to suspension polymerization to prepare a modified styrene resin (B). After sufficiently drying the obtained bead-shaped resin, the resin was dissolved in methyl ethyl ketone, and the intrinsic viscosity was measured in a thermostat at 30 ° C .. As a result, it was 0.60 dl / g. [Reference Example 3] The contents of the polyester resin (C) used in the examples are as follows.

C-1: Toray PBT resin “Toray PBT1”
100S ".

C-2: PET resin "J02" manufactured by Mitsui Chemicals, Inc.
5 Reference Example 4 The phenolic resin (D) used in the examples is as follows.

D: Phenol novolak resin “PR53195” manufactured by Sumitomo Durez. Reference Example 5 The contents of red phosphorus (E) used in the examples are as follows. In addition, the conductivity is as follows: 5 g of red phosphorus and 100 m of pure water.
l, and the mixture was extracted in an autoclave at 121 ° C. for 100 hours. After red phosphorus was filtered, the filtrate was diluted to 250 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 component (F-
1 to F-3) were prepared as follows.

F-1: polyester resin (C-1) 10
0 parts by weight, 43 parts by weight of red phosphorus (E-1) were mixed, and a nitrogen flow was carried out.
Melt extrusion at a resin temperature of 270 ° C using a coaxial rotating twin screw extruder (DEX: 45.5, manufactured by Nippon Seiko Co., Ltd.) with a /D=45.5, and a high phosphorus content of polyester resin with red phosphorus concentration of 30% by weight Was prepared.

F-2: Polyester resin (C-1) 10
With respect to 0 parts by weight, 43 parts by weight of red phosphorus (E-2) was mixed, and a red phosphorus high concentration product of a polyester resin having a red phosphorus concentration of 30% by weight was prepared in the same manner.

F-3: Nylon resin (G) 10 described below
With respect to 0 parts by weight, 43 parts by weight of red phosphorus (E-1) was mixed, and a high concentration of red phosphorus of a nylon resin having a red phosphorus concentration of 30% by weight was prepared in the same manner. [Reference Example 7] Nylon resin (G) used in Examples is as follows.

G: Toray nylon resin "Amilan CM"
1010 "[Examples 1 to 5, Comparative Examples 1 to 6] According to the compounding ratios shown in Table 1, each component was adjusted to have a screw diameter of 30 mm and an L / D of 2
5 co-rotating twin screw extruder (PCM-3 manufactured by Ikegai Iron Works)
0) batch supply from the hopper port, resin temperature 250
The mixture was melt-extruded at 150 ° C. at 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.

[0079]

[Table 1]

[0080]

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

The styrene resin (A) of Examples 1 to 5, the modified styrene resin (B) obtained by copolymerizing an epoxy group-containing vinyl monomer, the polyester resin (C), the phenol resin (D) and the red The composition comprising phosphorus (E) is UL9
The flame retardancy of V-0 or more determined in Example 4 was obtained.
It can be seen that they have excellent flame retardancy, flexural modulus, bending stress, impact resistance and heat resistance as compared with the.

In particular, from the comparison between Example 1 and Comparative Example 1 and between Example 2 and Comparative Example 2, it was found that the addition of the modified styrene resin (B) copolymerized with an epoxy group-containing vinyl monomer caused combustion. It is clear that the performance is further improved.

From the comparison between Examples 2 and 3 and Comparative Example 3, it is clear that the flame retardancy decreases with the addition of the phenolic resin (D). Flame retardancy cannot be obtained.

From Examples 2 and 5, the average particle size was 30 μm.
It can be seen that the use of red phosphorus (E-1) having a conductivity of 200 μS / cm has a shorter burning time and is more advantageous.

In Comparative Example 4, since the content of the modified styrene resin (B) obtained by copolymerizing an epoxy group-containing vinyl monomer was excessive, the extrusion / moldability was inhibited by gelation,
A molded product could not be obtained by the production method under the above conditions.

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

As can be seen from Comparative Example 6, when the nylon resin (G) is used instead of the polyester resin (C), the desired flame retardancy cannot be obtained.

[0088]

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 67/00 67/00 F term (reference) 4F070 AA18 AA32 AA37 AA44 AA46 AA47 AB08 AC01 AC20 AE07 FA03 FB04 FC05 4J002 BC06W BC07W BC08W BC09W BC11W BC12X BG07X BH01W CC03 CC05 CD01X CD19X CF04Y CF05Y CF08Y CF09Y CF13Y CF14Y DA056 FA006 FB076 FB086 FD020 FD030 FD050 FD070 FD100 GFD136 FD170 G

Claims (7)

[Claims] 1. A styrene resin (A) in an amount of 20 to 98 parts by weight, a modified styrene resin (B) obtained by copolymerizing an epoxy group-containing monomer in an amount of 1 to 40 parts by weight, and a polyester resin (C) in an amount of 1 to 60 parts by weight. A flame-retardant resin composition comprising 1 to 30 parts by weight of a phenolic resin (D) and 1 to 10 parts by weight of red phosphorus (E) per 100 parts by weight of a resin composition comprising: 2. The flame-retardant resin composition according to claim 1, wherein the styrene resin (A) is a rubber-modified styrene resin. 3. The conductivity of the red phosphorus (E) when it is extracted in hot water (100 g of pure water is added to 5 g of red phosphorus and extracted in an autoclave at 121 ° C. for 100 hours, for example).
The flame-retardant resin composition according to claim 1 or 2, wherein the filtrate after red phosphorus filtration has an electrical conductivity (extracted water obtained by diluting the filtrate to 250 ml) in the range of 0.1 to 1000 µS / cm. 4. The flame-retardant resin composition according to claim 1, wherein the content of red phosphorus having a particle size of 75 μm or more in the red phosphorus (E) is 10% by weight or less. 5. A resin component selected from the styrene resin (A), a modified styrene resin (B) obtained by copolymerizing an epoxy group-containing vinyl monomer, and a polyester resin (C), Resin composition (F) having a high red phosphorus concentration by melt-kneading the whole or a part of red phosphorus (E) once
The flame retardant according to any one of claims 1 to 4, wherein, after the resin composition is produced, the remaining resin component and the resin composition (F) having a high red phosphorus concentration are melt-kneaded by an extruder. A method for producing a conductive resin composition. 6. A resin composition (F) having a high red phosphorus concentration by once melt-kneading at least a part of the polyester resin (C) and the whole or a part of the red phosphorus (E). 6. The method for producing a flame-retardant resin composition according to claim 5, wherein the remaining resin component and the resin composition (F) having a high red phosphorus concentration are melt-kneaded by an extruder. 7. A molded article comprising the flame-retardant resin composition according to claim 1.