JPH11335513A - Flame-retardant thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition excellent in flame retardancy and resistance to falling weight impact in thin-wall applications and suitable for thin-wall molded articles by admixing a specific organic phosphorous compound, a phenolic resin and a colorant with a rubber-reinforced styrenic resin. SOLUTION: This resin composition comprises 100 pts.wt. of (A) a rubber- reinforced styrenic resin, 1-20 pts.wt. of (B) an organic phosphorous compound represented by formula I, 0.1-10 pts.wt. of (C) a phenolic resin and 0.1-5 pts.wt. of (D) a colorant, the wt. ratio of the components C to D being 90:10 to 10:90. In the formulae I-IV, R<1> -R<8> are the same or different and are each H or 1-5C alkyl; Ar<1> -Ar<4> are the same or different and are each phenyl or phenyl substituted with an organic residue free of a halogen; X is formulae II, III or IV; Y is a direct bond, O, S, SO2 , C(CH3 )2 , CH2 , CHPh (wherein Ph is phenyl); n is an integer at least 0; k and m are each an integer of 0-2; and k+m is an integer of 0-2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent flame retardancy, impact resistance, rigidity, heat resistance, and moldability, and is particularly excellent in flame retardancy in thin-walled materials and falling weight impact. The present invention relates to a thermoplastic resin composition suitable for a product.

[0002]

2. Description of the Related Art Plastics have excellent mechanical properties,
Due to its moldability and electrical insulation, it is used in a wide range of fields including home electric appliances, OA appliances, automobiles and other parts. However, in recent years, most of plastics used in such fields are flammable, and there is an increasing demand for flame retardancy due to safety issues, and various flame retardant technologies have been devised.

[0003] Generally, a method is employed in which a halogen-based flame retardant such as a bromine compound having a high flame-retardant efficiency and antimony oxide are blended with a resin to make the resin flame-retardant. However, the use of flame retardants that do not contain chlorine and bromine has become highly desirable due to environmental impact.

Heretofore, as a method of making a thermoplastic resin flame-retardant without using a chlorine or bromine-based flame retardant, a method of blending red phosphorus and a metal oxide with a styrene resin (Japanese Patent Laid-Open No.
106140), a method of blending red phosphorus and an organic phosphorus compound (JP-A-4-106142), a method of blending an aromatic phosphate ester with a rubber-reinforced styrene resin (JP-A-8-337703), A method of blending a phosphorus compound and a phenol resin with a thermoplastic resin (JP-A-8-208884) has been proposed.

[0005]

However, the method using a halogen-based flame retardant has a problem of environmental pollution because a gas is generated by decomposition of a halogen compound at the time of molding or burning.

Further, the composition disclosed in JP-A-4-106140 has poor impact resistance and molding processability.
The composition described in JP-B-142 is not satisfactory because of its poor heat resistance.

The composition described in JP-A-8-337703 has insufficient heat resistance and the flame retardancy of a thin molded product is poor, and the composition described in JP-A-8-208884 has poor impact resistance. Thus, these did not satisfy various properties.

The present invention is a resin which is excellent in flame retardancy, impact resistance, rigidity, heat resistance and molding processability, and is particularly excellent in flame retardancy and falling weight impact with a thin wall and suitable for a thin wall molded article. It is intended to provide a composition.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present invention has revealed that a specific organic phosphorus compound, a phenolic resin and an inorganic colorant are contained in a rubber-reinforced styrene resin at a specific ratio. By blending in a specific amount, it has been found that the flame retardancy and heat resistance, which are excellent in the flame-extinguishing property, the moldability and the impact of the thin falling weight are remarkably excellent.

That is, the present invention relates to "(A) 100 parts by weight of a rubber-reinforced styrene resin, (B) 1 to 20 parts by weight of an organic phosphorus compound represented by the general formula (1), (C) phenolic resin 0.1 to 10 parts by weight, (D) coloring agent 0.1 to 5
Parts by weight, and the weight ratio of (C) and (D) is 9
A flame-retardant thermoplastic resin composition having a ratio of 0:10 to 10:90.

Embedded image (In the above formula, R ^{1 to} R ⁸ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.
r ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different phenyl groups or phenyl groups substituted with halogen-free organic residues. Y is a direct bond, O, S, S
O ₂ , C (CH ₃ ) ₂ , CH ₂ , and CHPh, and Ph represents a phenyl group. N is an integer of 0 or more. 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. ) ".

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The weight in the present invention means mass.

The rubber-reinforced styrenic resin (A) in the present invention has a structure in which a (co) polymer containing a styrene monomer is grafted to a rubbery polymer, and a resin containing a styrene monomer. It also includes those having a structure in which the (co) polymer is not grafted to the rubbery polymer.

More specifically, 95 to 20 parts by weight of a monomer or monomer mixture containing (a1) an aromatic vinyl monomer in an amount of 20% by weight or more per 5 to 80 parts by weight of a rubbery polymer (b) (A1) 5 to 100% by weight of a graft (co) polymer obtained by graft polymerization and (a2) a monomer or monomer mixture containing at least 20% by weight of an aromatic vinyl monomer. (A2) vinyl-based (co) polymer 0 to 95
% By weight is preferred.

As the rubbery polymer (b), those having a glass transition temperature of 0 ° C. or less are preferred, and diene rubbers are preferably used. Specifically, diene rubbers such as polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-butadiene block copolymer, butyl acrylate-butadiene copolymer, and acrylics such as polybutyl acrylate Rubber, polyisoprene, ethylene-propylene-diene terpolymer and the like. Among them, polybutadiene or butadiene copolymer is preferred.

The gel content of the rubbery polymer is preferably at least 50%, more preferably at least 60%, from the viewpoint of impact resistance and gloss of the resin composition. If necessary, no gel was measured when measured with a toluene solvent, or loose gel, for example, JSR0561 manufactured by Nippon Synthetic Rubber Co., Ltd., Nipol 4850A manufactured by Nippon Zeon Co., Ltd. % By weight or less can be used.

The rubber particle diameter of the rubbery polymer is not particularly limited, but the weight average particle diameter of the rubber particles is 0.15 to 2.0.
μm, particularly 0.20 to 1.0 μm, is preferable because of excellent impact resistance.

The average weight particle size of the rubber particles is "Ru
bber Age Vol. 88p. 484-490
(1960) by E.I. Schmidt, P .; H. B
sodium salt alginate method described in “Idison” (particles having a cumulative weight fraction of 50% from the cumulative weight fraction of the creamed weight ratio and the sodium alginate concentration utilizing the fact that the particle size of polybutadiene to be creamed varies depending on the concentration of sodium alginate) (Determining the diameter).

As the aromatic vinyl monomer, styrene,
Examples include α-methylstyrene, vinyltoluene, o-ethylstyrene, pt-butylstyrene, etc., with styrene being particularly preferred.

As monomers other than the aromatic vinyl monomers, vinyl cyanide monomers are used for the purpose of further improving impact resistance, and (meth) acrylic monomers are used for the purpose of improving toughness and color tone. Acid ester monomers are preferably used. Examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like, and acrylonitrile is particularly preferable. Examples of the (meth) acrylate-based monomer include methyl and ethyl esters of acrylic acid and methacrylic acid with ethyl, propyl, n-butyl and i-butyl. Particularly, methyl methacrylate is preferred.

If necessary, other vinyl monomers,
For example, maleimide monomers such as maleimide, N-methylmaleimide, and N-phenylmaleimide can be used.

The monomer or monomer mixture used in the (A1) graft (co) polymer is preferably at least 20% by weight of an aromatic vinyl monomer from the viewpoint of the impact resistance of the resin composition. It is preferably at least 50% by weight. When a vinyl cyanide monomer is mixed, the amount is preferably 60% by weight or less, and more preferably 50% by weight or less, from the viewpoint of moldability of the resin composition. When a (meth) acrylate monomer is mixed, toughness,
From the viewpoint of impact resistance, the content is preferably 80% by weight or less, and more preferably 75% by weight or less. The total amount of the aromatic vinyl-based monomer, vinyl cyanide-based monomer and (meth) acrylate-based monomer in the monomer or monomer mixture is preferably 95 to 20% by weight, and Preferably it is 90 to 30% by weight.

(A1) The ratio of the rubbery polymer to the monomer mixture in obtaining the graft (co) polymer is preferably at least 5 parts by weight of the rubbery polymer based on 100 parts by weight of the total graft copolymer. , More preferably at least 10 parts by weight,
The amount is preferably 0 parts by weight or less, more preferably 70 parts by weight or less. From the viewpoint of the impact resistance of the resin composition, the proportion of the rubbery polymer is preferably at least 5 parts by weight, and the impact resistance and the appearance of the molded article are not impaired.
0 parts by weight or less is preferred.

The (A1) graft (co) polymer can be obtained by a known polymerization method. For example, it can be obtained by a method in which a mixture of a monomer and a chain transfer agent and a solution of a radical generator dissolved in an emulsifier are continuously supplied to a polymerization vessel in the presence of a rubbery polymer latex to carry out emulsion polymerization.

(A1) The graft (co) polymer contains a non-grafted copolymer in addition to a material obtained by grafting a monomer or a monomer mixture to a rubbery polymer. It is. (A) The graft ratio of the graft (co) polymer is not particularly limited, but is preferably from 20 to 200% by weight, particularly preferably from 25 to 150% by weight in order to obtain a resin composition having excellent impact resistance and gloss. . Here, the graft ratio is calculated by the following equation.

Graft ratio (%) = <amount of vinyl copolymer graft-polymerized on rubbery polymer> / <rubber content of graft copolymer> × 100

The properties of the non-grafted (co) polymer are not particularly limited, but the intrinsic viscosity [η] (measured at 30 ° C.) of the methyl ethyl ketone-soluble component is 0.25-0.
6 dl / g, especially in the range of 0.25 to 0.5 dl / g,
Since a resin composition having excellent impact resistance can be obtained, it is preferably used.

(A1) The graft (co) polymer has a structure in which a (co) polymer containing at least 20% by weight of an aromatic vinyl monomer is individually contained in the rubbery polymer particles (occluded structure). It is preferable to use a rubbery polymer having the following in order to improve the flame retardancy, falling weight impact strength and heat resistance in a well-balanced manner.

The above-mentioned occlude structure is a structure in which one or more (co) polymer particles containing 20% by weight or more of an aromatic vinyl monomer having a size of 0.01 μm or more are contained in a rubbery polymer.

In order to exhibit the effects of the present invention efficiently, the rubbery polymer having an occluded structure containing 5 or more, preferably 10 or more, of the above (co) polymer particles with respect to all the rubbery polymers is used. It is preferable to contain 10% or more on average.

The occluded structure can be observed, for example, with an electron microscope under ultrathin sections of a resin composition dyed with osmic acid.

(A2) The vinyl (co) polymer is a copolymer essentially containing an aromatic vinyl monomer. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, vinyltoluene, o-ethylstyrene, and the like, with styrene being particularly preferred. One or more of these can be used.

As a monomer other than the aromatic vinyl monomer, a vinyl cyanide monomer is preferably used for the purpose of further improving impact resistance. For the purpose of improving toughness and color tone, (meth) acrylate monomers are preferably used. Examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like, and acrylonitrile is particularly preferable.
(Meth) acrylic ester monomers include acrylic acid and methacrylic acid methyl, ethyl, propyl, n
Examples thereof include an esterified product with -butyl and i-butyl, and methyl methacrylate is particularly preferable.

As other vinyl monomers copolymerizable therewith, maleimide monomers such as maleimide, N-methylmaleimide and N-phenylmaleimide can be used as required.

(A2) From the viewpoint of the impact resistance of the resin composition, the proportion of the aromatic vinyl monomer as a component of the vinyl (co) polymer is preferably at least 20% by weight based on all monomers. Preferably, it is more preferably at least 50% by weight. When a vinyl cyanide monomer is mixed, the content is preferably 60% by weight or less, more preferably 50% by weight or less, from the viewpoint of impact resistance and fluidity. When a (meth) acrylate monomer is mixed, the amount is preferably 80% by weight or less, more preferably 75% by weight or less from the viewpoint of toughness and impact resistance. When other vinyl monomers copolymerizable therewith are mixed, the content is preferably 60% by weight or less, more preferably 50% by weight or less.

Although the characteristics of the vinyl (co) polymer are not limited, the intrinsic viscosity [η] (methyl ethyl ketone solvent, 30 ° C.
Measurement) is 0.40 to 0.65 dl / g, especially 0.45
０．５0.55 dl / g, N, N-dimethylformamide solvent, and 0.30 when measured at 30 ° C.
5 to 0.85 dl / g, especially 0.45 to 0.70 dl / g
Those having a range of g are preferable because a resin composition having excellent impact resistance and moldability can be obtained.

The method for producing the vinyl (co) polymer is not particularly limited, and includes a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, and a bulk polymerization method.
Conventional methods such as a suspension polymerization method and a solution-bulk polymerization method can be used.

The organic phosphorus compound (B) used in the present invention is a phosphoric ester represented by the following general formula (1).

[0038]

Embedded image

In the above formula (1), n is an integer of 0 or more. K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less. Preferably, k and m are each an integer of 0 or more and 1 or less, particularly preferably k or m. Is 1.

In the formula (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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-
Butyl group, n-isopropyl, neopentyl, tert
A pentyl group, 2-isopropyl, neopentyl, te
rt-pentyl group, 3-isopropyl, neopentyl,
a tert-pentyl group, neoisopropyl, neopentyl, tert-pentyl group and the like.
A methyl group and an ethyl group are preferable, and hydrogen is particularly preferable.

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

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

One or more of the above organic phosphorus compounds can be used arbitrarily by changing the ratio.

(B) The method for producing the organic phosphorus compound is not particularly limited. For example, after reacting phosphorus oxychloride and hydroquinone in a solvent at a substantially 2: 1 molar ratio, 2,6-
Hydroquinone-bis (2,6-dimethylphenyl) phosphate can be obtained by adding an appropriate amount of dimethylphenol and reacting.

In the present invention, when (B) an organic phosphorus compound is blended, (A) 100 parts by weight of the resin composition
0.1 to 20 parts by weight, preferably 1 to 20 parts by weight, more preferably 5 to 15 parts by weight. When the amount of the organic phosphorus compound (B) is within the above range, flame retardancy and moldability are improved.

The phenolic resin (C) 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 modified resins thereof Resins. 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, falling weight impact strength, and economy.

The shape is not particularly limited, and any of pulverized products, granules, flakes, powders, needles, and liquids can be used.

The phenolic resin (C) can be used alone or in combination of two or more, if necessary.

(C) The phenolic resin is not particularly limited, and commercially available resins can be used. For example, in the case of a novolak type phenol resin, phenols and aldehydes are charged into a reaction tank at a molar ratio of 1: 0.7 to 1: 0.9, and oxalic acid, hydrochloric acid,
After adding a catalyst such as sulfuric acid or toluenesulfonic acid, the mixture is heated and refluxed for a predetermined time. Vacuum dehydration or static dehydration to remove generated water, and further, a method of removing remaining water and unreacted phenols can be obtained. The co-condensed phenol resin obtained by using these resins or a plurality of raw material components can be used alone or in combination of two or more.

In the case of a resole type phenol resin,
The molar ratio of phenols to aldehydes is 1: 1 to 1: 2
After charging into a reaction tank in such a ratio as follows, adding a catalyst such as sodium hydroxide, aqueous ammonia, and other basic substances, the same reaction and treatment as for the novolak-type phenol resin can be performed.

Here, phenols are phenol, o
-Cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butylcatechol, catechol, isoeugenol, o-
Methoxyphenol, 4,4'-dihydroxyphenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate, 2,6-di-tert
-Butyl-p-cresol and the like. One or more of these phenols can be used.
On the other hand, aldehydes include formaldehyde, paraformaldehyde, polyoxymethylene, trioxane and the like. One or more of these aldehydes can be used as needed.

The molecular weight of the phenolic resin is not particularly limited, but is preferably in the range of 200 to 2,000 in number average, and particularly in the range of 400 to 1,500 is excellent in mechanical properties, moldability and economical efficiency. preferable. The phenolic resin can be measured by gel permeation chromatography using a tetrahydrafuran solution and a phenol resin standard sample.

The colorant (D) used in the present invention is not particularly limited, and any known one can be used as needed. Examples thereof include organic pigments such as carbon black, titanium oxide, red iron oxide, and ultramarine blue. And organic dyes. These colorants are used to improve compatibility with resins, silane coupling agents, surfactants,
Those which have been surface-treated with a lubricant, silicon oxide or the like are also included.

As the colorant, a mixture of titanium oxide such as titanium white and an optional pigment and, if necessary, a fluorescent whitening agent is used.

In the present invention, when (C) a phenolic resin is blended, 0.1 to 10 parts by weight, preferably 0.2 to 8 parts by weight, more preferably 100 parts by weight of the resin composition (a). Is 0.5 to 5 parts by weight. (C)
When the amount of the phenolic resin is within the above range, the flame retardancy becomes good.

When (D) a colorant is blended in the present invention, (A) 100 parts by weight of the resin composition
0.1 to 5 parts by weight, preferably 0.5 to 5 parts by weight, more preferably 1 to 4 parts by weight. (D) When the amount of the coloring agent is within the above range, the Izod impact strength becomes good.

Further, in order to exert the effect of the present invention, the weight ratio of the phenolic resin (C) to the colorant (D) is 90:10 to 10:90, preferably 80:20 to 2.
0:80, more preferably 75:25 to 40:60, and even more preferably 70:30 to 40:60. When the weight ratio of (C) and (D) is in the above range, the compatibility between (A) the resin composition and (C) the phenolic resin and (D) the colorant is improved, and the flame retardancy and the thinness are improved. The drop weight impact strength and the heat resistance are extremely good.

Further, a radical generator (E) can be used if necessary. As the radical generator (E),
There is no particular limitation as long as it is a compound that generates a radical by light or heat, but a compound such as —O—O— bond, —C—C
Compounds having any one type of chemical bond can be used. Among such radical generators, those that do not generate radicals during melting compound but generate radicals during combustion are preferable in order to obtain a high effect as a flame retardant. For this purpose, the radical generator used in the present invention has a one-minute half-life of 200 ° C.
Or more, more preferably 250 ° C.
That's all.

The one-minute half-life can be measured by a known method. 0.1 mol of radical generator
% Benzene solution, sealed in a glass ampoule purged with nitrogen, attached to a thermostat set at a predetermined temperature (T), and thermally decomposed. Assuming that the thermal decomposition time at this time is t, the concentration of the decomposed radical generator is X, the initial concentration of the radical generator is a, and the decomposition rate constant is k, lna / (ax) = kt (4) Holds.

Here, since the half-life is the time until the concentration of the radical generator decreases to half of the initial value due to the generation of radicals, the half-life is represented by t _1/2 and the relationship of X = a / 2. By substituting into the above equation, kt _1/2 = ln2 (5) is obtained.

Accordingly, thermal decomposition is carried out at a certain temperature, the relationship between time t and lna / (ax) is plotted, k is obtained from the slope of the obtained straight line, and t _{1 / 2} can be measured. The above measurement was measured at several temperatures (T), the relationship between t _1/2 and 1 / T obtained from each was plotted, and the decomposition temperature at 1 minute half life was measured from the obtained straight line. be able to.

Preferred (C) radical generators include
Specific examples include a compound represented by the following general formula (2).

[0063]

Embedded image Here, in the above formula, R ^{9 to} R ¹⁴ represent the same or different hydrogen atoms or monovalent organic residues having 1 to 10 carbon atoms.

Here, specific examples of the monovalent organic residue having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. Groups, n-pentyl group, 2-pentyl group, 3-pentyl group, neopentyl group, allyl group, phenyl group, xylyl group, cumenyl group, naphthyl group, etc., and methyl group, ethyl group, and phenyl group are preferable. Particularly, a methyl group and a phenyl group are preferable.

Among the radical generators represented by the general formula (2), those represented by the following general formula (3) can be more preferably used in terms of flame retardancy.

[0066]

Embedded image Here, in the above formula, R ^{10 to} R ¹³ represent the same or different hydrogen atoms or monovalent organic residues having 1 to 10 carbon atoms.

The monovalent organic residue having 1 to 10 carbon atoms specifically includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl. Groups, n-pentyl group, 2-pentyl group, 3-pentyl group, neopentyl group, allyl group, phenyl group, xylyl group, cumenyl group, naphthyl group, etc., and methyl group, ethyl group, and phenyl group are preferable. Particularly, a methyl group and a phenyl group are preferable.

In the present invention, when (E) a radical generator is compounded, (A) 100 parts by weight of the resin composition,
It is at most 5 parts by weight, preferably at most 0.01 to 3 parts by weight, more preferably at most 0.05 to 1 part by weight. (E)
When the amount of the radical generator is within the above range, flame retardancy and Izod impact strength can be further improved.

In the present invention, a higher fatty acid amide may be added for the purpose of further enhancing the drip-extinguishing property and the falling weight impact of a thin molded article.

Examples of higher fatty acid amides include stearic acid monoamide, stearic acid bisamide, lauric acid bisamide, lauric acid ethylene bisamide, stearic acid ethylene bisamide, hydroxystearic acid bisamide, hydroxystearic acid ethylene bisamide, and particularly stearic acid. Ethylene bisamide, hydroxystearic acid ethylene bisamide and lauric acid ethylene bisamide have excellent flame retardancy and impact resistance, and can be suitably used.

The method for producing the flame-retardant resin plastic composition of the present invention is not particularly limited. For example, (A) a rubber-reinforced styrene resin, (B) an organic phosphorus compound, (C) a phenolic resin and (D) It is prepared by supplying a colorant to an extruder or the like with or without premixing, and sufficiently melting and kneading in a temperature range of 150 to 300 ° C. In this case, the product is produced by melt-kneading using, for example, a single-screw having a “Dalmage” type screw, a twin-screw having a changed screw shape, a multi-screw extruder, a roll, a kneader, or the like.

The flame-retardant thermoplastic resin composition of the present invention can contain this and another thermoplastic resin. For example, polyphenylene ether, polycarbonate, polyglutarimide, polycyclohexane dimethylene terephthalate, etc. are mixed to improve impact resistance and heat resistance.Polyolefin, polybutylene terephthalate, polyethylene terephthalate, etc. are mixed to improve chemical resistance. be able to. If necessary, fillers such as glass fibers, antioxidants such as phenylisodecyl phosphate, various stabilizers such as ultraviolet absorbers, lubricants and plasticizers can be added in necessary amounts.

The flame-retardant thermoplastic resin composition of the present invention is melt molded and used as a resin molded product. This resin molded article has excellent drip-extinguishing property at a molded article thickness of 0.5 to 3 mm, especially 2 mm or less, exhibits flame resistance of V-2 or more according to UL94 standard, and has excellent falling weight impact of a thin molded article. From the characteristics, printer, PC, display, CRT display, fax, copy, word processor, notebook PC, DVD drive, PD drive, floppy disk drive, etc., DVD drive, PD drive , Related parts of storage devices such as floppy disk drives, liquid crystal display parts, FDD carriages, FDD
Chassis HDD parts, electrical and electronic parts such as computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, audio parts, audio equipment parts such as audio, laser disks, and compact disks Useful for lighting parts, refrigerator parts, air conditioner parts.

[0074]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples. In the examples, the number of parts and% indicate parts by weight and% by weight, respectively, and the unit "" means inches (1 inch = 2.54 cm).

Reference Example 1 (A1) Preparation of Rubber Reinforced Styrenic Resin A method for preparing a rubber reinforced styrene resin is described below. The graft ratio was determined by the following method. Acetone was added to a predetermined amount (m) of the graft copolymer and refluxed for 4 hours. This solution is cooled to 8000 rpm (480 × 10 ³ s ⁻¹ ).
(Acceleration 10,000G (about 100 × 10 ³ m / s ² ))
After centrifugation for 30 minutes, insoluble matter was filtered. This insoluble content is 7
It dried under reduced pressure at 0 degreeC for 5 hours, and measured the weight (n).

Graft ratio = [(n)-(m) × L] /
[(M) × L] × 100 Here, L means the rubber content of the graft copolymer.

<A1-1> A monomer mixture 40 composed of 72% styrene and 28% acrylonitrile in the presence of 60 parts (in terms of solids) of polybutadiene latex (average rubber particle diameter 0.3 μm, gel content 85%) And then emulsion polymerization was carried out. The obtained graft copolymer is coagulated with sulfuric acid,
The mixture was neutralized with caustic soda, washed, filtered and dried to prepare a powdery graft copolymer <A1-1>. The obtained graft copolymer had a graft ratio of 36%. This graft copolymer contained 17.9% of a non-graft copolymer composed of 72% of styrene structural units and 28% of acrylonitrile. The intrinsic viscosity of the soluble portion of methyl ethyl ketone was 0.33 dl / g.

<A1-2> 35 parts of polybutadiene (average rubber particle diameter 0.23 μm, gel content 80%) (in terms of solid matter), styrene-butadiene copolymer rubber copolymerized with 25% styrene (average rubber particles) Styrene 7 in the presence of 10 parts (solid content) with a diameter of 0.61 μm and a gel content of about 0%.
Monomer mixture 5 consisting of 4% and 26% acrylonitrile
Emulsion polymerization was conducted by adding 5 parts. The obtained graft copolymer was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to prepare a powdery graft copolymer <A1-2>. The obtained graft copolymer has a graft ratio of 39%.
Met. This graft copolymer contained 37% of a non-graft copolymer composed of 74% of styrene structural units and 26% of acrylonitrile. In addition, the intrinsic viscosity in a methyl ethyl ketone solvent is 0.421 dl /
g.

REFERENCE EXAMPLE 2 (A2) Preparation of vinyl copolymer A monomer mixture composed of 72% of styrene and 28% of acrylonitrile was subjected to suspension polymerization to prepare a vinyl copolymer.
The intrinsic viscosity of the obtained vinyl copolymer in a methyl ethyl ketone solvent was 0.51.

Reference Example 3 (B) Organophosphorus Compound <B-1> PX200 (manufactured by Daihachi Chemical Co., Ltd.) which is resorcinol bis (di-2,6-dimethylphenyl) phosphate was used.

<B-2> Triphenyl phosphate was used.

Reference Example 4 (C) Phenolic Resin PR53195 (manufactured by Sumitomo Durez Co., Ltd.), which is a non-thermally reactive phenol novolak resin having a number average molecular weight of 700, was used.

REFERENCE EXAMPLE 5 (D) Colorant Gray colorant CN46 containing titanium white as a main component.
4 (manufactured by Nippon Pigment Co., Ltd.) was used.

Reference Example 6 (E) Radical generator An example using 2,3-diphenyl-2,3-dimethylbutane (Nofuma BC, manufactured by NOF Corporation) having a one-minute half-life temperature of 330 ° C. (A) rubber-modified styrene resin prepared in Reference Examples 1 to 14,
(B) an organic phosphorus compound, (C) a phenolic resin, (D)
The colorant and the (E) radical generator were mixed at the compounding ratio shown in Table 1, and melt-kneaded and extruded at a resin temperature of 220 ° C. with a vented 30 mmφ twin-screw extruder.
A pellet-shaped polymer was produced. Next, a test piece was molded by an injection molding machine at a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C., and the physical properties were measured under the following conditions. Table 3 shows the results.

[0085] 1/2 "Izod impact strength: ASTM
D256-56A.

Deflection temperature under load: ASTM D648 (load: 1.82 MPa) Impact strength of falling weight: 5R for a disk-shaped product (40φ × 2 mmt)
The weight having the tip is dropped, and the height at which the test piece breaks by 50% and the weight of the weight at that time are determined.

MFR: JIS K7210 (230 ° C.,
(Load: 2.16 kgf (21.18 N)) A larger value means better fluidity during molding.

Flame retardancy: A vertical combustion test was performed in accordance with UL94 standard. The test piece had a thickness of 1.5 mm.

Comparative Examples 1 to 10 (A) Rubber-modified styrenic resin prepared in Reference Example,
(B) an organic phosphorus compound, (C) a phenolic resin, (D)
The coloring agents were mixed at the compounding ratios shown in Table 2, and the respective physical properties were measured in the same manner as in the examples. Table 4 shows the measurement results.

[0090]

[Table 1]

[0091]

[Table 2]

[0092]

[Table 3]

[0093]

[Table 4]

The following is clear from the results of Tables 3 and 4. All of the resin compositions of the present invention (Examples 1 to 14) are excellent in impact resistance, fluidity, flame retardancy, heat resistance, particularly in thin-walled flame retardancy and falling weight impact resistance.

On the other hand, when the amount of the organic phosphorus compound (B) is less than 1 part by weight (Comparative Example 1), the flame retardancy is poor, and when it exceeds 20 parts by weight (Comparative Example 2), the heat resistance is poor. Not preferred.

When the weight ratio of the (C) phenolic resin to the (D) colorant was out of the range of 90:10 to 10:90 (Comparative Examples 3, 4, 9, and 10), Or, the impact resistance is deteriorated, which is not preferable.

(C) The compounding amount of the phenolic resin is 0.1
When the amount is less than 10 parts by weight (Comparative Example 7), the impact resistance is deteriorated.

(D) When the amount of the coloring agent is less than 0.1 part by weight (Comparative Example 6), the impact resistance and flame retardancy are poor, and when it exceeds 5 parts by weight (Comparative Example 8), the impact resistance is It is not preferable because the property deteriorates.

[0099]

The flame-retardant thermoplastic resin composition of the present invention comprises:
It does not necessarily require bromine or chlorine compounds, and exhibits excellent flame retardancy and impact resistance, especially flame retardancy of thin-walled molded articles, falling weight impact strength, heat resistance, and moldability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // (C08L 51/04 61:06) (C08L 55/02 61:06)

Claims (11)

[Claims] (A) 100 parts by weight of a rubber-reinforced styrene resin, (B) 1 to 20 parts by weight of an organic phosphorus compound represented by the general formula (1), and (C) phenolic resin 0.1 to 100 parts by weight. 10
Parts by weight, (D) 0.1 to 5 parts by weight of a coloring agent, and the weight ratio of (C) and (D) is 90:10 to 10:90.
A flame-retardant thermoplastic resin composition, characterized in that: Embedded image (In the above formula, R ^{1 to} R ⁸ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.
r ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different phenyl groups or phenyl groups substituted with halogen-free organic residues. Y is a direct bond, O, S, S
O ₂ , C (CH ₃ ) ₂ , CH ₂ , and CHPh, and Ph represents a phenyl group. N is an integer of 0 or more. 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. ) 2. The composition according to claim 1, wherein the phenolic resin (C) is a phenol novolak resin which is non-thermally reactive and has a number-average molecular weight of 200 to 2,000. Flame retardant thermoplastic resin composition. 3. The phenolic resin (C) has a softening temperature of 70.
The flame retardant thermoplastic resin composition according to claim 2, wherein the temperature is from 200 to 200C. 4. A colorant comprising titanium oxide or a mixture of titanium oxide and a pigment or dye.
The flame-retardant thermoplastic resin composition according to any one of the above. 5. A rubber having a structure in which (A) a rubber-reinforced styrene-based resin has an occluded (co) polymer containing at least 20% by weight of an aromatic vinyl-based monomer inside rubbery polymer particles. The flame-retardant thermoplastic resin composition according to any one of claims 1 to 4, which is a resin composition containing 1 to 30 parts by weight of a porous polymer. 6. The flame retardant according to claim 1, further comprising (E) 0.01 to 5 parts by weight of a radical generator per 100 parts by weight of the rubber-reinforced styrene resin. Thermoplastic resin composition. 7. The (E) radical generator has a one-minute half-life of 20 minutes.
The flame-retardant resin composition according to claim 6, wherein the temperature is 0 ° C or higher. 8. The radical generator (C) represented by the following general formula (2)
The flame-retardant thermoplastic resin composition according to claim 6 or 7, wherein Embedded image (In the above formula, R ^{9 to} R ¹⁴ represent the same or different hydrogen atoms or monovalent organic residues having 1 to 10 carbon atoms.) 9. The method according to claim 1, wherein (E) the radical generator is represented by the following formula (3)
The flame-retardant thermoplastic resin composition according to claim 6 or 7, wherein Embedded image (In the above formula, R ^{10 to} R ¹³ represent the same or different hydrogen atoms or monovalent organic residues having 1 to 10 carbon atoms.) 10. A test piece having a flame retardancy based on UL94 standard of V-2 at a thickness of 0.5 to 3.0 mm.
The flame-retardant thermoplastic resin composition according to any one of claims 1 to 9, wherein: 11. An injection-molded article comprising the flame-retardant thermoplastic resin composition according to claim 1 and having a minimum thickness of 2 mm or less.