JP2000351881A - Flame-retardant resin composition and molded article made thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin composition which has a high flame retardancy and is excellent in mechanical properties and heat resistance by compounding a styrene resin with specified amounts of an inorganic filler and red phosphorus. SOLUTION: A styrene resin in an amount of 100 pts.wt. is compounded with 1-50 pts.wt. inorganic filler and 0.1-20 pts.wt. red phosphorus. An AS resin and a modified AS resin are especially preferable as the styrene resin. The modified AS resin is a copolymer of an aromatic vinyl monomer, (meth) acrylonitrile, and another vinyl monomer. Glass fibers and a glass powder are preferable as the inorganic filler. Red phosphorus used here is preferably one prepared by coating unground red phosphorus with aluminum hydroxide and then with a phenolic thermosetting resin and, when subjected to extraction in hot water, preferably has an electrical conductivity of 0.1-1,000 μS/cm. Preferably, the composition further contains at least one resin selected from phenolic resins and phenoxy resins.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition which imparts high flame retardancy to a styrene resin without using a halogen-based organic compound, and has excellent mechanical properties and heat resistance. Related to molded products.

[0002]

2. Description of the Related Art Styrene resins typified by ABS resin and AS resin are used in a wide range of fields such as household electric equipment, OA equipment, and automobiles due to their excellent moldability, surface appearance and mechanical properties. Have been. On the other hand, since styrene resins are extremely flammable among thermoplastic resins, flame resistance is often required due to safety issues.

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 into the resin is generally used. However, in connection with recent environmental problems, a flame-retardant resin containing no halogenated organic compound has been strongly desired.

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. In this method, a desired flame retardancy is imparted. Requires a large amount of flame retardants.

Further, a method of adding red phosphorus is disclosed in
Japanese Patent Application Laid-Open No. 9-296119 discloses a method of further adding heat-expandable graphite and red phosphorus to JP-A No. 108248, but the resin composition obtained by the present invention has a small effect of improving flame retardancy. In particular, styrene resins were insufficient.

[0006]

That is, the present invention provides a flame-retardant resin composition which imparts a high degree of flame retardancy to a styrene resin without using a halogen-based organic compound, and has excellent mechanical properties and heat resistance. The task is to get things.

[0007]

Means for Solving the Problems In view of the above situation, the present inventors have made intensive studies and as a result, by adding an inorganic filler and red phosphorus to a styrene-based resin, it has high flame retardancy. And
Further, it has been found that a flame-retardant resin composition having excellent mechanical properties and heat resistance can be obtained.

That is, the present invention provides "(A) 100 parts by weight of a styrene resin, (B) 1 to 50 parts by weight of an inorganic filler,
(C) A flame-retardant resin composition comprising 0.1 to 20 parts by weight of red phosphorus. ".

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant resin composition of the present invention will be specifically described below.

(A) The styrene resin is a polymer containing an aromatic vinyl monomer as a component. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene, o-ethylstyrene, o-chlorostyrene and o, p-dichlorostyrene. But
Particularly, styrene and α-methylstyrene are preferably used. These may be used alone or in combination of two or more.

Further, for the purpose of imparting properties such as chemical resistance and heat resistance to the styrene resin, another vinyl monomer copolymerizable with an aromatic vinyl monomer may be copolymerized. As these vinyl monomers, acrylonitrile, methacrylonitrile and ethacrylonitrile, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, ( N-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, chloromethyl (meth) acrylate, glycidyl (meth) acrylate,
Maleic anhydride, itaconic anhydride, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and the like can be mentioned, and acrylonitrile is particularly 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 those having a mass of from 300,000 to 300,000 in order to maintain the balance of physical properties. The weight average molecular weight can be measured by a generally known method using gel permeation chromatography (hereinafter abbreviated as GPC).

In order to improve the impact resistance of the styrene resin, a rubber-reinforced styrene resin in which rubber polymer particles are dispersed in the styrene resin may be used. 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 preferably 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 and isoprene rubber can be used.

Here, since the rubbery polymer and the styrene resin as the matrix are incompatible, the impact resistance can be further improved by grafting a component compatible with the matrix to the rubbery polymer. it can. 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 a 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, and the composition and the graft amount are not particularly limited, but do not impair the dispersibility of the rubbery polymer. It is preferable to adjust the composition and the graft amount as described above.

As a specific example of the above styrene resin,
Polystyrene, high-impact polystyrene, AS resin, modified AS resin, AAS resin, AES resin, ABS resin, etc. are included. From the viewpoint of flame retardancy, acrylonitrile is contained as a copolymer component, and mechanical properties and moldability are improved. Resin, ABS resin, and modified AS having an excellent balance of are preferred, and particularly preferred are AS resin and modified AS resin. Here, the modified AS resin refers to one or more of an aromatic vinyl monomer and (meth) acrylonitrile and another vinyl monomer copolymerizable with the aromatic vinyl monomer. It means a copolymer with a vinyl monomer.

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.

Also, the method of grafting an aromatic vinyl monomer and another monomer copolymerizable therewith to a rubbery polymer can be produced by conventionally known emulsion polymerization or bulk polymerization. Although it is possible, it is advantageous to produce it by emulsion polymerization in terms of quality.

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

The (B) inorganic filler used in the present invention comprises:
It is a reinforcing material of thermoplastic resin made of inorganic substance, while improving the mechanical strength and heat resistance of styrene resin,
When used in combination with red phosphorus, the flame retardancy of the styrene resin is drastically increased.

Examples of the inorganic filler (B) include glass fiber, glass powder, glass beads, glass flake, alumina, alumina fiber, carbon fiber, graphite fiber,
Examples include stainless steel fiber, whisker, potassium titanate fiber, wollastenite, asbestos, hard clay, calcined clay, talc, kaolin, mica, calcium carbonate, magnesium carbonate, aluminum oxide and minerals. From the viewpoint of the effect of improving the flame retardancy, glass fibers and glass powder are preferably used.

The inorganic filler (B) is not particularly limited, and those generally used as a reinforcing material for a thermoplastic resin can be used. These may be used alone or in combination of two or more.

The amount of the inorganic filler (B) used in the present invention is 1 to 100 parts by weight of the styrene resin (A).
５０50 parts by weight, preferably 5-40 parts by weight, more preferably 10-30 parts by weight. If the amount of the inorganic filler (B) is less than 1 part by weight, the flame retardancy, mechanical properties and heat resistance are insufficient, and if it exceeds 50 parts by weight, the moldability is remarkably deteriorated and injection molding may not be possible.

The red phosphorus (C) used in the present invention is unstable as it is, and has the property of gradually dissolving in water or reacting gradually with water. What has been applied is preferably used. As a method for treating such red phosphorus, the method of pulverizing red phosphorus described in JP-A-5-229806 is not performed, and a red crushed surface having high reactivity with water and oxygen is not formed on the surface of red phosphorus. A method of finely dividing phosphorus, a method of catalytically suppressing oxidation of red phosphorus by adding a small amount of aluminum hydroxide or magnesium hydroxide to red phosphorus,
A method of coating red phosphorus with paraffin or wax to suppress contact with moisture, a method of stabilizing by mixing with ε-caprolactam or trioxane, a method of mixing red phosphorus with phenolic, melamine, epoxy, or unsaturated polyester A method of stabilizing by coating with a thermosetting resin such as, red phosphorus is treated with an aqueous solution of a metal salt such as copper, nickel, silver, iron, aluminum and titanium to deposit a metal phosphorus compound on the surface of the red phosphorus. Method to stabilize, red phosphorus aluminum hydroxide, magnesium hydroxide, titanium hydroxide,
Examples include a method of coating with zinc hydroxide or the like, a method of stabilizing the surface of red phosphorus by electroless plating with iron, cobalt, nickel, manganese, tin, or the like, and a method of combining them. A method of pulverizing red phosphorus without forming a crushed surface on the surface of red phosphorus without pulverizing the phosphorus, phenol-based, melamine-based, epoxy-based red phosphorus,
A method of stabilizing by coating with a thermosetting resin such as an unsaturated polyester system, aluminum hydroxide, aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide,
A method of stabilizing by coating with red or the like, particularly preferably a method of pulverizing red phosphorus without pulverizing the red phosphorus and forming a crushed surface on the surface, a method of converting red phosphorus to a phenolic or melamine-based This is a method of stabilizing by coating with a thermosetting resin such as an epoxy-based or unsaturated polyester-based resin, or a combination of both. 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 resin. The unground red phosphorus refers to red phosphorus produced without forming a crushed surface.

Among such red phosphorus, it is particularly preferable that pulverization of the red phosphorus is not performed, 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 pulverized red phosphorus with aluminum hydroxide or magnesium hydroxide and further coated with a phenolic thermosetting resin or an epoxy type thermosetting resin is most preferred, and particularly preferred is hydroxylation of unground red phosphorus. Red phosphorus coated with aluminum and further coated with a phenolic thermosetting resin is preferred.

The average particle size of red phosphorus before being blended with the resin is from 35 to 0. 0 from the viewpoint of flame retardancy, mechanical properties, and chemical and physical deterioration of red phosphorus due to pulverization during recycling.
01 μm is preferred, and more preferably 30 to
It is 0.1 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 size, that is, red phosphorus having a particle size of 75 μm or more, contained in red phosphorus 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 as possible.

Here, the content of red phosphorus having a particle diameter of 75 μm or more contained in red phosphorus can be measured by classifying the particles using a 75 μm mesh. That is, 100 g of red phosphorus
From the residual amount A (g) when classifying with a 5 μm mesh,
The content of red phosphorus having a particle size of 75 μm or more is A / 100 × 100
(%).

The conductivity of the red phosphorus (C) used in the present invention when it is 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,
And 0.1 to 1000 μS /
cm, preferably 0.1 to 800 μS / cm, more preferably 0.1 to 500 μS / cm.

Examples of such 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.

In the present invention, the amount of red phosphorus (C) added is 0.1 to 20 parts by weight based on 100 parts by weight of the styrene resin (A).
Parts by weight, preferably 1 to 15 parts by weight, more preferably 5 to 10 parts by weight. If the amount of red phosphorus (C) is less than 0.1 part by weight, the flame retardancy is insufficient, and if it exceeds 20 parts by weight, the styrene resin composition itself becomes brittle and practical mechanical properties cannot be obtained. There are cases.

In the present invention, it is preferable to use one or more resins selected from (D) phenolic resins and phenoxy resins for the purpose of further improving flame retardancy.

The phenolic resin 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-reactive resins, or resins obtained by modifying these, may be used. No. These are uncured resins without curing agents, semi-cured resins,
Alternatively, it may be a cured resin. Above all, a phenol novolak resin which does not contain a curing agent and is non-thermally reactive is preferred in terms of flame retardancy and economy. The shape is not particularly limited, and any of pulverized 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 economy. The number average molecular weight of the phenolic resin can be measured by a GPC method using a tetrahydrafuran solution.

One or more of the above phenolic resins can be used as necessary.

The phenoxy resin used in the present invention refers to a phenoxy resin or a phenoxy copolymer obtained by reacting an aromatic dihydric phenol compound with epichlorohydrin at various mixing ratios.
It is represented by the following general formula (1).

[0037]

Embedded image (Where X is a direct bond, O, S, SO ₂ , C (C
H ₃ ) ₂ , CH ₂ and CHPh, and Ph represents a phenyl group. The molecular weight of the phenoxy resin is not particularly limited, but may be 1,000 to 1,000 in terms of polystyrene equivalent number average molecular weight.
000, and especially those in the range of 11,000 to 25,000 are preferably used from the viewpoints of moldability and economy. The number average molecular weight of the phenoxy resin can be measured by a GPC method using a tetrahydrafuran solution.

One or more of the above-mentioned phenoxy resins can be used as necessary.

The addition amount of one or more resins (D) selected from the phenolic resins and phenoxy resins used in the present invention is 100 styrene resins (A).
The amount is 1 to 30 parts by weight, preferably 3 to 20 parts by weight, more preferably 5 to 10 parts by weight with respect to parts by weight.

Further, to the flame-retardant resin composition of the present invention, a phosphoric acid ester may be further added in order to enhance flame retardancy and moldability. The phosphoric ester used here is represented by the following formula (2).

[0041]

Embedded image In the formula (2), n is an integer of 0 or more, preferably 0 to 10, and particularly preferably 0 to 5. The upper limit is preferably 40 or less from the viewpoint of flame retardancy.

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, and preferably, k and m are each an integer of 0 or more and 1 or less;
Particularly preferably, k and m are each 1.

R ^{1 to} R ⁸ 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 methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-isopropyl, neopentyl Tert-pentyl group, 2-isopropyl, neopentyl, tert-pentyl group,
Examples thereof include 3-isopropyl, neopentyl, tert-pentyl, neoisopropyl, neopentyl, and tert-pentyl. Of these, hydrogen, methyl, and ethyl are preferable, and hydrogen is particularly preferable.

Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ represent the same or different aromatic groups or aromatic groups substituted with halogen-free organic residues. As the aromatic group, an aromatic group having a benzene skeleton, a naphthalene skeleton, an indene skeleton, or an anthracene skeleton is preferable, and an aromatic group having a benzene skeleton or a naphthalene skeleton is preferable. These may be substituted with an organic residue containing no halogen (preferably an organic residue having 1 to 8 carbon atoms), and the number of substituents is not particularly limited, but may be 1 to 3. preferable. Specific examples include a phenyl group,
Examples thereof include aromatic groups such as a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a naphthyl group, an indenyl group, and an anthryl group.A phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a naphthyl group are preferable, and a phenyl group is particularly preferable. , A tolyl group and a xylyl group are preferred. Z is a direct bond,
O, S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CHPh, and Ph represents a phenyl group.

The above phosphoric esters may be used alone or in combination of two or more. The amount of the phosphate ester used is usually 0.1 to 30 parts by weight based on 100 parts by weight of the styrene resin (A) from the viewpoints of mechanical properties, heat resistance, moldability, and flame retardancy.
It can be used in parts by weight.

The flame-retardant resin composition of the present invention may further contain carbon black and a coloring agent. here,
The carbon black and the colorant are pigments that can be generally blended with the thermoplastic resin, and the amount of the pigment is 0.01 to 30 parts by weight based on 100 parts by weight of the styrene resin (A). 0.05 from the viewpoint of flame retardancy and mechanical properties
It is preferably added in the range of 10 to 10 parts by weight.

Further, the flame retardant resin composition of the present invention may contain a triazine compound and a salt of cyanuric acid or isocyanuric acid. Such a triazine-based compound and a salt of cyanuric acid or isocyanuric acid are an adduct of cyanuric acid or isocyanuric acid and a triazine-based compound, and are usually 1 to 1 (molar ratio). Alternatively, the salt of isocyanuric acid is an adduct of cyanuric acid or isocyanuric acid with a triazine-based compound, and is usually an addition having a composition of 1: 1 (molar ratio), and sometimes 1: 2 (molar ratio). Things.

Examples of the above triazine compounds include melamine, benzoguanamine, acetoguanamine, 2-amide-4,6-diamino-1,3,5-triazine, mono (hydroxymethyl) melamine, di (hydroxymethyl) melamine, Tri (hydroxymethyl) melamine and the like.

The salt of the triazine compound and the cyanuric acid or isocyanuric acid was prepared by mixing a mixture of the triazine compound and the cyanuric acid or isocyanuric acid with a water slurry and mixing them well to form fine particles of both salts. Thereafter, this slurry is a powder obtained by filtering and drying, and is different from a mere mixture. This salt does not need to be completely pure, and an unreacted triazine compound or cyanuric acid or isocyanuric acid may remain.

The average particle size of the salt before being mixed with the resin may be 0.01 to 100 μm from the viewpoint of flame retardancy, mechanical strength and surface properties of the molded product. If the salt has poor dispersibility, a dispersant such as tris (β-hydroxyethyl) isocyanurate may be used in combination.

Further, the flame-retardant resin composition of the present invention may be used, depending on the purpose, as a phosphorus-based, phenol-based stabilizer, phenol-based, phosphite-based or sulfur-based antioxidant, hindered phenol-based, benzotriazole-based. -Based, benzophenone-based, benzoate-based and cyanoacrylate-based ultraviolet absorbers, waxes, higher fatty acids and acid esters and acid amides, and lubricants and plasticizers such as higher alcohols,
Amine-based, sulfonic acid-based, polyether-based antistatic agents and the like can also be added.

The flame-retardant resin composition of the present invention is usually produced by a known method. One or more resins selected from styrene resins (A), inorganic fillers (B), red phosphorus (C), (D) phenolic resins, and phenoxy resins;
There is no particular limitation on the method of melt-kneading other necessary additives, as long as mechanical shearing in a molten state of a styrene resin such as a single-screw extruder, a twin-screw extruder or a kneader can be performed. Preferably, an extruder which 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. When an extruder is used, a method in which all components are supplied from a feed port, or a method in which a styrene resin (A) and red phosphorus (C) are supplied from a feed port on the upstream side of the extruder and an inorganic filler (B )
There is no particular limitation on the supply method such as the method for supplying the components from the downstream feed port. Before the raw materials are supplied to an extruder or the like, they may be mixed in a blender or the like in advance.

Here, when an extruder is used, particularly from the viewpoints of productivity, operability, safety, dispersibility of red phosphorus, flame retardancy of the flame retardant resin composition obtained, and mechanical properties. A part of the finally mixed resin component and the whole or a part of the red phosphorus (C) are once melt-kneaded to produce a resin composition (E) having a high red phosphorus concentration, and the remaining resin components ( D) One or more resins selected from phenolic resins and phenoxy resins, a resin composition (E) having a high red phosphorus concentration, and optionally other additives that can be optionally used. A method of melt-kneading with an extruder is preferably used.

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

Specific examples of the “part of the resin component finally mixed” include “part or all of the styrene resin (A)” and “1 selected from phenol resin and phenoxy resin. Part or all of the seed or two or more resins (D) ".

The red phosphorus high concentration product (E) composed of the styrene resin (A) is preferably 20 to 200 parts by weight of red phosphorus (C) based on 100 parts by weight of the styrene resin.

The red phosphorus high-concentration product (E) comprising one or more resins selected from phenol resins and phenoxy resins includes one or two resins selected from phenol resins and phenoxy resins. The amount of the red phosphorus (C) is preferably 20 to 200 parts by weight based on 100 parts by weight of the resin.

As the high-concentration red phosphorus product (E) composed of a phenolic resin, a powder mixture of a powdery phenolic resin and red phosphorus (C) can also be used.

The flame-retardant resin composition thus obtained can be usually molded by a known method, and it should be molded articles such as injection molding, extrusion molding and compression molding, and molded articles of all shapes such as sheets and films. Can be. Among them, it is particularly suitable for use in injection molded products. It is also suitable for molded articles having a complicated shape such as molded articles having a weld portion and a hinge section, insert molded articles, and thin molded articles, and is suitable for various mechanical mechanism parts, electric and electronic parts, or automobile parts.

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 -Home and office electrical product parts such as laser disk (registered trademark) and compact disk, audio equipment parts, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. 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, motor parts, lighters, typewriters, etc. Optical components such as microscopes, binoculars, cameras, clocks, etc., precision machinery components, alternator terminals, alternator connectors, IC regulators, potentiometer bases for light drier, various valves such as exhaust gas valves, 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, Rake 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, 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 insulating plate, Step motor rotor , Lamp socket, lamp reflector, lamp housing, brake piston, solenoid It is useful for various applications such as bobbins, engine oil filters, ignition device cases, play equipment, toiletries, entertainment, toys, chemical plants, aviation parts, etc. It can be used as household electrical equipment, OA equipment parts and housings, and automobile parts.

[0061]

EXAMPLES Hereinafter, the effects of the present invention will be described in more detail with reference to examples. Here, all parts are parts by weight. 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. The flame retardancy was evaluated according to the evaluation criteria set forth in. The flame retardancy level decreases in the order of V-0>V-1>V-2> HB. In addition, in the case of evaluation of V-2 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 a Toshiba Machine's IS55EPN injection molding machine at a molding temperature of 250 ° C. and a mold temperature of 60 ° C. AS
The flexural modulus and flexural stress were measured according to TM 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.
According to STM D-648 (load: 1.82 MPa),
The deflection temperature under load (DTUL) was measured.

Reference Example 1 The styrene resin (A) used in the present invention is 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 "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: Toray's ABS resin “Toyolac 5”
00 ”.

Reference Example 2 The inorganic filler (B) used in the present invention is as follows.

B-1: Glass fiber "T-
340 / P "B-2: Nippon Electric Glass Glass Powder" EPG-M7
0E ".

Reference Example 3 The red phosphorus (C) used in the present invention is as follows. In addition,
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, diluting the solution after filtering the red phosphorus to 250 mL, and measuring the conductivity with a conductivity meter (Personal SC manufactured by Yokogawa Electric Corporation). Meter).

C-1: Red phosphorus “Nova Excel 140” manufactured by Rin Kagaku Kogyo Co., Ltd., obtained by coating unmilled red phosphorus with aluminum hydroxide and further coating with a thermosetting phenol resin, having an average particle diameter of 30 μm and a conductivity of 200 μS / cm C. -2: Rinka Kagaku Kogyo "Nova Red 120", which is obtained by coating pulverized red phosphorus with magnesium hydroxide and further coated with a thermosetting phenol resin, having an average particle size of 38 μm, a conductivity of 1200 μS / cm, and a particle size of 7
Red phosphorus content of 5 μm or more 15%.

Reference Example 4 The resin (D) used in the present invention is as follows.

D-1: Phenol novolak resin "PR53195" manufactured by Sumitomo Durez D-2: Phenoxy resin "Phenotote Y" manufactured by Toto Kasei
P-50 ".

Reference Example 5 The red phosphorus high concentration product (E) used in the present invention is as follows.

E-1: Red phosphorus "NOVA EXCEL 140" manufactured by Rin Kagaku Kogyo Co., Ltd. of 43 was used as red phosphorus (C) for 100 parts by weight of the styrene resin produced in A-1.
Parts and mixing with nitrogen flow, screw diameter 3
Resin temperature of 25 using a coaxial rotary twin screw extruder (TEX-30, manufactured by Nippon Steel Co., Ltd.) of 0 mm and L / D = 45.5.
The mixture was melt-extruded at 0 ° C. to prepare a high-concentration styrene-based resin (E-1) having a red phosphorus concentration of 30%.

E-2: 100 parts by weight of phenol novolak resin “PR53195” manufactured by Sumitomo Durez and 100 parts of C-1 red phosphorus “Nova Excel 140” manufactured by Rin Kagaku Kogyo Co., Ltd. were mixed as red phosphorus (C). The mixture was mixed with a Henschel mixer while flowing nitrogen, and a phenol novolak resin having a red phosphorus concentration of 50% and a red phosphorus high concentration powder product (E-
2) was adjusted.

E-3: 100 parts by weight of D-2 phenoxy resin “Phenotote YP-50” manufactured by Toto Kasei,
As red phosphorus (C), 100 parts of red phosphorus "NOVA EXCEL 140" manufactured by Rin Kagaku Kogyo Co., Ltd. of C-1 was mixed, and a nitrogen flow was carried out, while the screw diameter was 30 mm and L / D was 45.5.
Coaxial rotary twin screw extruder (TEX-3, manufactured by Nippon Steel Corporation)
Using 0), a high-concentration phenoxy resin (E-3) having a red phosphorus concentration of 50% was prepared by melt extrusion at a resin temperature of 180 ° C.

Examples 1 to 7 and Comparative Examples 1 to 4 Each component was mixed according to the mixing ratio shown in Table 1 with a screw diameter of 30.
The co-rotating twin-screw extruder (PCM-30, manufactured by Ikegai Iron Works) having a mm and an L / D of 25 was supplied collectively from a hopper port and melt-extruded at a resin temperature of 250 ° C. and a screw rotation speed of 150 rpm. After drying the obtained pellets at 80 ° C. for 3 hours,
It was subjected to injection molding to form a target test piece. The evaluation results are also shown in Table 1.

[0080]

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

(A) Styrene resin of Examples 1 to 7,
The composition comprising (B) an inorganic filler and (C) red phosphorus is
Comparative Example 1 with flame retardancy of V-1 or more specified in L94
It can be seen that they have excellent flame retardancy, flexural modulus, bending stress, impact resistance and heat resistance as compared with those of Comparative Example 1. In particular, those using the AS resin from Examples 1 and 3 have a shorter combustion time,
Higher flame retardancy can be obtained. In Comparative Example 3, although the flexural modulus, bending stress, impact resistance and heat resistance are high,
No flame retardancy was obtained.

From the comparison between Examples 1 and 5, the conductivity was 200 μm.
It can be seen that those using red phosphorus, which is S / cm, have an extremely short burning time and are particularly excellent in flame retardancy. Furthermore, as compared with Examples 1, 7 and 6, the resin composition to which a phenol resin or a phenoxy resin is added has higher flame retardancy.

From Comparative Example 2, 100% of the inorganic filler (B) was used.
In the present example, the addition of parts by weight was inferior in moldability so that injection molding was impossible. Also, from Comparative Example 4,
(C) Although injection molding can be carried out with the addition of 30 parts by weight of red phosphorus, the molded article was brittle and could not be used for evaluation, that is, practical mechanical strength could not be obtained.

Examples 8 to 10 Instead of red phosphorus (C), the red phosphorus high-concentration product (E) shown in Reference Example 5 was used, and each component was mixed according to the composition shown in Table 2 with a screw diameter of 30 mm, L / L D is 25 and co-rotating twin screw extruder (PCM-30 manufactured by Ikegai Tekko Co., Ltd.).
Melt extruded at pm. The obtained pellets were dried at 80 ° C. for 3 hours and then subjected to injection molding to form a target test piece. The evaluation results are also shown in Table 2. The amounts of the styrene resin, the phenolic resin, the phenoxy resin, and the amount of red phosphorus in the red phosphorus high concentration product are described in the section of the red phosphorus high concentration product in the table. When a red phosphorus high concentration product (E-1) made of a styrene resin was used as the high phosphorus phosphorus concentration product, it was added so that the amount of the styrene resin in the resin composition became 100 parts.

[0085]

[Table 2] Example 1 using red phosphorus (C), Example 8 using red phosphorus high concentration (E-1) composed of styrene resin, and high phosphorus concentration (E-2) composed of phenolic resin From the comparison of Example 9, it was found that the one using the high-concentration red phosphorus product had a tendency to shorten the burning time and improve the mechanical strength.

Also, from a comparison between Example 7 using red phosphorus (C) and Example 10 using a high-concentration red phosphorus product (E-3) made of a phenoxy resin, the product using the high-concentration red phosphorus product was ,
There is a tendency that the burning time is shortened and the mechanical strength is also improved.

[0087]

The present invention provides a styrene resin with high flame retardancy without using a halogenated organic compound,
Another object is to obtain a resin composition having excellent mechanical strength and heat resistance.

The flame-retardant resin composition and the molded product obtained by the present invention are suitable for home electric appliances, OA appliances, automobile parts, housings and the like.

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Claims (7)

[Claims] 1. 100 parts by weight of a styrene resin (A), 1 to 50 parts by weight of an inorganic filler (B), and 0.1 to 20 parts of red phosphorus (C).
A flame-retardant resin composition comprising parts by weight. 2. One or more resins (D) selected from phenolic resins and phenoxy resins.
The flame-retardant resin composition according to claim 1, which contains 0 parts by weight. 3. The styrenic resin (A) is an AS resin, ABS
The flame-retardant resin composition according to claim 1, wherein the composition is one or more selected from a resin and a modified AS resin. 4. The flame-retardant resin composition according to claim 1, wherein the inorganic filler (B) is glass fiber and / or glass powder. 5. The red phosphorus (C) has a conductivity of 0.1 to 1000 μm.
The flame-retardant resin composition according to claim 1, wherein the composition is S / cm. 6. The flame-retardant resin according to claim 1, wherein the red phosphorus (C) is red phosphorus obtained by coating unground red phosphorus with aluminum hydroxide and further coating with a thermosetting phenol resin. Composition. 7. A molded article comprising the flame-retardant resin composition according to claim 1.