JP2000336226A - Flame retarded resin composition manufacture thereof and molded article therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame retarded styrene-based resin compsn. which not only furnishes a high level flame retardance without using a halogen-based org. compd. but also is excellent in mechanical properties and heat resistance, a manufacturing method therefor and a molded article therefrom. SOLUTION: This flame retarded resin compsn. is obtd. by blending 100 pts.wt. of a styrene-based resin (A), 1-50 pts.wt. of a PBT (polybutylene terephthalate) resin (B), 1-50 pts.wt. of an inorg. filler (C) and 0.1-20 pts.wt. of red phosphorus (D). It is desirable to further blend 1-30 pts.wt. of one or more resins (E) selected from th group consisting of a phenol resin and a phenoxy 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, since styrene resins are extremely flammable among thermoplastic resins, flame retardancy 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 is generally used. In the case of a resin composition containing, there is a problem that a large amount of smoke is generated at the time of combustion. In view of recent environmental problems, it is strongly desired to realize a flame-retardant resin composition containing no halogenated organic compound. It is supposed to be.

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

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

[0007]

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

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

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that a styrene-based resin can be replaced with a polybutylene terephthalate resin (hereinafter referred to as PB).
It is called T resin. ), A specific amount of an inorganic filler and a specific amount of red phosphorus have been found to provide a flame-retardant resin composition having high flame retardancy and excellent mechanical properties and heat resistance.

That is, the flame-retardant resin composition of the present invention comprises:
For 100 parts by weight of the styrene resin (A), 1 to 50 parts by weight of the PBT resin (B), 1 to 50 parts by weight of the inorganic filler (C) and 0.1 to 20 parts by weight of red phosphorus (D) are blended. It is characterized by becoming.

The method for producing a flame-retardant resin composition according to the present invention is a method for melt-kneading a styrene resin (A), a PBT resin (B), an inorganic filler (C) and red phosphorus (D) with an extruder. It is characterized by doing.

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

[0013]

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

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

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

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

Further, in order to improve the impact resistance of the styrene resin, a rubber-reinforced styrene resin obtained by dispersing rubbery polymer particles 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 60% by weight or more, especially 75% by weight.
The above is preferred. Specifically, polybutadiene rubber, styrene-butadiene copolymer, hydrogenated styrene-butadiene rubber, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer, isoprene rubber, and the like can be used.

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

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

Here, the modified AS resin is one or two types of aromatic vinyl monomers and (meth) acrylonitrile, and other vinyl monomers copolymerizable with the aromatic vinyl monomers. It means a copolymer with at least one kind of 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.

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

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

The PBT resin (B) used in the present invention is a thermoplastic polyester containing terephthalic acid and 1,4-butanediol as main components. The degree of polymerization of the PBT resin is not particularly limited, but the intrinsic viscosity measured at 25 ° C. in a 0.5% o-chlorophenol solution is 0.20.
80 to 1.9, particularly preferably 1.0 to 1.5.

In the present invention, the amount of the PBT resin (B) added is 100 parts by weight of the styrene resin (A).
The amount is 1 to 50 parts by weight, preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight. If the added amount of the PBT resin (B) is less than 1 part by weight, the flame retardancy and mechanical properties are insufficient, and if it exceeds 50 parts by weight, problems such as warpage of molded articles occur, and excellent molding of styrene resin is performed. It is not preferable because processability may be impaired.

The inorganic filler (C) used in the present invention is a reinforcing material for a thermoplastic resin composed of an inorganic substance, and improves the mechanical strength and heat resistance of the styrene resin (A). , Red phosphorus (D)
It has the function of dramatically increasing the flame retardancy of the styrene resin (A).

Specific examples of such an inorganic filler (C) include glass fiber, glass powder, glass beads, glass flake, alumina, alumina fiber, carbon fiber, graphite fiber, stainless steel fiber, whisker, potassium titanate fiber. , Walastenite, asbestos, hard clay, calcined clay, talc, kaolin, mica, calcium carbonate,
Examples thereof include magnesium carbonate, aluminum oxide, and minerals. From the viewpoint of the reinforcing effect of the styrene resin (A) and the effect of improving flame retardancy, glass fibers and glass powder are particularly preferably used.

The type of the inorganic filler (C) 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 (C) in the present invention is 1 to 5 with respect to 100 parts by weight of the styrene resin (A).
0 parts by weight, preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight. If the amount of the inorganic filler (C) 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 molding processability is remarkably deteriorated, and injection molding cannot be performed. Therefore, it is not preferable.

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

Among such red phosphorus, it is particularly preferable to pulverize the red phosphorus without pulverizing the red phosphorus, 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 the red phosphorus before being blended with the resin is from 35 to 35 in terms of flame retardancy, mechanical properties, and chemical and physical deterioration of the red phosphorus due to pulverization during recycling.
It is preferably 0.01 μm, more preferably 3 μm.
The thickness is from 0 to 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 diameter contained in red phosphorus, that is, red phosphorus having a particle diameter of 75 μm or more significantly reduces flame retardancy, mechanical properties and recyclability. Therefore, red phosphorus having a particle size of 75 μm or more is preferably removed by classification or the like. The content of red phosphorus having a particle size of 75 μm or more is from the viewpoint of flame retardancy, mechanical properties and recyclability.
10% by weight or less, more preferably 8% by weight
Or less, particularly preferably 5% by weight or less. The lower limit is not particularly limited, but is preferably as close to 0 as possible.

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

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

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 to these commercial products.

The amount of red phosphorus (D) used in the present invention 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 (D) 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 are obtained. This is not preferred because it may not be possible.

In the present invention, it is preferable to use one or more resins (E) selected from 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 are used. No. These may be an uncured resin, a semi-cured resin, or a cured resin without a curing agent added. 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 of the phenol resin is not particularly limited, and any of crushed products, granules, flakes, powders, needles, and liquids can be used.

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

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

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).

[0044]

Embedded image (Where X is a direct bond, O, S, SO ₂ , C (CH
₃ ) represents any one of 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 particularly those in the range of 11,000 to 25,000 are preferably used from the viewpoint of moldability and economy. The number average molecular weight of the phenoxy resin can be measured by a GPC method using a tetrahydrafuran solution.

The above-mentioned phenoxy resin may be used, if necessary,
Species or two or more can be used.

The addition amount of one or more resins (E) selected from the phenolic resins and phenoxy resins used in the present invention is as follows.
1 to 30 parts by weight, preferably 3 to 20 parts by weight, per 100 parts by weight
Parts by weight, more preferably 5 to 10 parts by weight.

Further, to the flame retardant resin composition of the present invention, a phosphate 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).

[0048]

Embedded image In the above formula (2), n is an integer of 0 or more, preferably 0
From 10 to 10, particularly preferably from 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 to 2 and k + m is an integer of 0 to 2; preferably, k and m are each an integer of 0 to 1; m is 1 each.

Further, R ^{1 to} R ⁸ are hydrogen or a compound having 1 to 1 carbon atoms.
5 represents any one of the alkyl groups, which may be the same or different from each other. Here, specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-isopropyl, Neopentyl group, tert-pentyl group, 2-isopropyl group, neopentyl group, tert-pentyl group, 3-isopropyl group, neopentyl group, tert-pentyl group,
Neoisopropyl group, neopentyl group and tert-
Although a pentyl group and the like are mentioned, hydrogen, a methyl group and an ethyl group are preferable, and hydrogen is particularly preferable.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each represent an aromatic group or an aromatic group substituted by a halogen-free organic residue, which are the same or different from each other. May be. Examples of such an aromatic group include aromatic groups having a benzene skeleton, a naphthalene skeleton, an indene skeleton, and an anthracene skeleton. Among them, those having a benzene skeleton or a naphthalene skeleton are 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 aromatic groups such as phenyl, tolyl, xylyl, cumenyl, mesityl, naphthyl, indenyl and anthryl, but phenyl, tolyl, xylyl, cumenyl and A naphthyl group is preferred, and a phenyl group, a tolyl group and a xylyl group are particularly preferred. Furthermore, Y
Is a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ , C
H ₂ represents 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 100 parts by weight based on the styrene resin (A) from the viewpoint of mechanical properties, heat resistance, moldability and flame retardancy.
It can be used in 30 parts by weight.

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 the thermoplastic resin, and the amount of the carbon black and the colorant is 0.01 to 30 parts by weight based on 100 parts by weight of the styrene resin (A). From the viewpoint of color, flame retardancy and mechanical properties,
It is preferably added in the range of 0.05 to 10 parts by weight.

Further, the flame-retardant resin composition of the present invention comprises
A salt of a triazine compound and cyanuric acid or isocyanuric acid may be blended. Such a triazine-based compound and a salt of cyanuric acid or isocyanuric acid,
It is an adduct of cyanuric acid or isocyanuric acid and a triazine-based compound, and is usually an adduct having a composition of 1: 1 (molar ratio), and sometimes 1: 2 (molar ratio).

Specific 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 and tri (hydroxymethyl) melamine.

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 an aqueous 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, cyanuric acid, or isocyanuric acid may remain.

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

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),
The method of melt-kneading the PBT resin (B), the inorganic filler (C), the red phosphorus (D) and other necessary additives is not particularly limited, and may be a single-screw extruder, a twin-screw extruder or a kneader. Any method and device capable of mechanically shearing a styrene resin in a molten state may be used. 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, a method in which all components are supplied from a feed port or a method in which a styrene resin (A), a PBT resin (B) and red phosphorus (D) are mixed on the upstream side of the extruder. There is no particular limitation on the supply method such as the method of supplying the inorganic filler (C) component from the downstream feed port through the feed port, and the productivity, red phosphorus dispersibility, and the resulting flame retardancy are not particularly limited. From the viewpoint of flame retardancy and mechanical properties of the resin composition,
A part of the resin component finally mixed and the whole or a part of the red phosphorus (D) are once melt-kneaded to produce a resin composition (F) having a high red phosphorus concentration, and the remaining resin component and inorganic filler are added. Agent (C)
A method of melt-kneading the resin composition (F) having a high red phosphorus concentration and optionally other additives as necessary by an extruder is preferably used.

Alternatively, a part of the resin component to be finally blended, red phosphorus (D) 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 concentration of red phosphorus than the amount of red phosphorus to be produced is produced, and a resin composition having a higher concentration of red phosphorus (F) and, if necessary, a resin composition having a higher concentration of red phosphorus. It is prepared by melt-kneading additives other than the optional additives added in the production stage of the product (F).

Specific examples of the “part of the resin component finally mixed” include “part or all of the styrene resin (A)” and “part or all of the PBT resin (B)”. Can be exemplified. In particular, a high-concentration product of red phosphorus composed of PBT resin (B) is most effective for exhibiting the effects of the present invention, and can dramatically improve the handling of red phosphorus, which is a conventionally dangerous substance. Can be used as a flame retardant for styrene resins. The composition of the flame retardant for a styrene resin is preferably 20 to 200 parts by weight of red phosphorus (D) based on 100 parts by weight of the PBT resin (B).

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

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

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

[0067]

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 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 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 Styrene resin "A-1" used in the present invention
The contents of “A-3” are 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, and a styrene resin “A-1” was obtained.
Was prepared. After sufficiently drying the obtained beaded 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 "A-3: A monomer composed of 61 parts by weight of styrene, 24 parts by weight of acrylonitrile, and 1 part by weight of glycidyl methacrylate was subjected to suspension polymerization in a polymerization tank equipped with a stirrer, and the modified styrene resin" A- 3 "was prepared. After sufficiently drying the obtained bead-like resin, it is dissolved in methyl ethyl ketone and
The intrinsic viscosity was measured in a 0 ° C.
It was 0 dl / g. [Reference Example 2] The contents of the PBT resin (B) used in the present invention are as follows.

B-1: Toray PBT resin “Toray PBT1”
100S "[Reference Example 3] The contents of the inorganic fillers" C-1 "and" C-2 "used in the present invention are as follows.

C-1: Glass fiber "T-
340 / P "C-2: Nippon Electric Glass Glass Powder" EPG-M7
0E "[Reference Example 4] Red phosphorus" D-1 "and" D "used in the present invention
The contents of "-2" are as follows. The conductivity was determined by adding 100 mL of pure water to 5 g of red phosphorus,
After performing an extraction treatment at 21 ° C. for 100 hours and filtering out red phosphorus, the filtrate was diluted to 250 mL and measured using a conductivity meter (Yokogawa Electric's personal SC meter).

D-1: Red phosphorus “Nova Excel 140” manufactured by Rin Kagaku Kogyo Co., Ltd. Average particle size 30 μm, conductivity 200 μS / cm D-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 5 Resins “E-1” and “E” used in the present invention
The contents of "-2" are as follows.

E-1: Phenol novolak resin "PR53195" manufactured by Sumitomo Durez E-2: Phenoxy resin "Phenotote Y" manufactured by Toto Kasei
P-50 "[Reference Example 6] Red phosphorus high concentration resin component" F-
"1" to "F-3" were prepared as follows.

F-1: 43 parts by weight of red phosphorus (D-1) is mixed with 100 parts by weight of the PBT resin (B-1), and while a nitrogen flow is performed, the screw diameter is 30 mm and L / D = 4.
5.5 coaxial rotary twin screw extruder (manufactured by Nippon Seiko, TE
X-30) was melt-extruded at a resin temperature of 270 ° C. to prepare a red phosphorus-enriched product “F-1” of a PBT resin having a red phosphorus concentration of 30%.

F-2: 100 parts by weight of PBT resin (B-1) was mixed with 43 parts by weight of red phosphorus (D-2), and red phosphorus of a PBT resin having a red phosphorus concentration of 30% was prepared in the same manner. A high concentration product "F-2" was prepared.

F-3: Nylon resin (G-1) shown below
43 parts by weight of red phosphorus (D-1) was mixed with 100 parts by weight, and a red phosphorus high concentration product "F-3" of a nylon resin having a red phosphorus concentration of 30% was prepared in the same manner. [Reference Example 7] The contents of the nylon resin (G-1) used in the present invention are as follows.

G-1: Toray nylon resin "Amilan"
CM1010 "[Examples 1 to 10, Comparative Examples 1 to 5] According to the compounding ratios shown in Table 1, each component was prepared with 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 250 ° C. and a screw rotation speed of 150 rpm. The obtained pellets were dried at 80 ° C. for 3 hours and then subjected to injection molding to form a target test piece. The physical property evaluation results of the test pieces are also shown in Table 1.

[0079]

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

The styrenic resins (A) of Examples 1 to 10,
PBT resin (B), inorganic filler (C) and red phosphorus (D)
Has a flame retardancy of V-1 or more specified in UL94, and has excellent flame retardancy, flexural modulus, flexural stress, impact resistance and heat resistance as compared with Comparative Example 1. You can see that it is. In particular, as can be seen from Examples 1, 3, and 4, those using the AS resin and the AS resin and the modified AS resin have a shorter burning time and higher flame retardancy. In Comparative Example 3 in which red phosphorus was not added, the flexural modulus, flexural stress, impact resistance, and heat resistance were high, but no flame retardancy was obtained.

According to the comparison between Examples 1 and 5 and 6, it was found that the use of the resin composition (F) having a high red phosphorus concentration, in which a part of the resin component and red phosphorus (D) were melt-kneaded beforehand, used flame retardant. It can be seen that the properties and impact resistance are good. Further, a comparison between Examples 1 and 8 shows that those using red phosphorus having a conductivity of 200 μS / cm have extremely short burning time and are particularly excellent in flame retardancy. Furthermore, by comparing Examples 1, 10 and 9,
It can be seen that a resin composition to which a phenol resin or a phenoxy resin is added has higher flame retardancy.

As can be seen from Comparative Example 2, the one to which 100 parts by weight of the inorganic filler (C) was added was inferior in moldability such that injection molding was impossible. In addition, as can be seen from Comparative Example 4, the one to which 30 parts by weight of red phosphorus (D) was added could be injection molded, but the molded article was brittle and could not be used for evaluation, and practical mechanical strength was obtained. I can't.

As can be seen from Comparative Example 5, the PBT
Those using nylon resin instead of resin (B)
The desired flame retardancy cannot be obtained.

[0084]

As described above, the flame-retardant resin composition of the present invention has high flame retardancy without using a halogenated organic compound, and exhibits excellent mechanical strength 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, OA appliances and automobile parts and housings.

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Claims (8)

[Claims] 1 to 100 parts by weight of a styrene resin (A), 1 to 50 parts by weight of a polybutylene terephthalate resin (B), 1 to 50 parts by weight of an inorganic filler (C), and 0.1 of red phosphorus (D). A flame-retardant resin composition comprising up to 20 parts by weight. 2. One or more resins (E) selected from phenolic resins and phenoxy resins
The flame-retardant resin composition according to claim 1, wherein 1 to 30 parts by weight is blended. 3. The method according to claim 1, wherein the styrene resin (A) is styrene /
The flame-retardant resin composition according to claim 1, wherein the composition is at least one selected from acrylonitrile copolymer resin (AS resin), ABS resin, and modified AS resin. 4. The flame-retardant resin composition according to claim 1, wherein the inorganic filler (C) is glass fiber and / or glass powder. 5. The red phosphorus (D) has a conductivity of 0.1 to 10.
The flame-retardant resin composition according to any one of claims 1 to 4, wherein the composition is 00 µS / cm. 6. The method according to claim 1, wherein the styrene resin (A), the polybutylene terephthalate resin (B), the inorganic filler (C) and the red phosphorus (D) are melt-kneaded by an extruder. A method for producing the flame-retardant resin composition according to any one of the preceding claims. 7. A resin composition (F) having a high red phosphorus concentration is produced by melt-kneading a part of the resin component to be finally mixed and the whole or a part of the red phosphorus (D) to obtain a resin composition (F) having a high red phosphorus concentration. Resin component, inorganic filler (C) and resin composition having high red phosphorus concentration (F)
7. The method for producing a flame-retardant resin composition according to claim 6, wherein the mixture is melt-kneaded with an extruder. 8. A molded article comprising the flame-retardant resin composition according to any one of claims 1 to 5.